Nitroimino-nitromethylene—azole or-azine heterocyclic compounds, insecticidal compositions containing them, and insecticidal methods of using them

ABSTRACT

Insecticides of the formula                    
     in which 
     n is 0 or 1, 
     X is S, O,                    
     or                    
     Y is N or                    
     Z is a 5- or 6-membered nitrogen-containing heterocyclic ring, and 
     R to R 9  variously represent hydrogen or specified organic radicals.

This application is a divisional of U.S. Ser. No. 09/012,620, filed Jan.23, 1998, now U.S. Pat. No. 6,022,967; which is a division of U.S. Ser.No. 08/662,096, filed Jun. 12, 1996, now U.S. Pat. No. 5,750,704; whichis a division of U.S. Ser. No. 08/404,849, filed on Mar. 15, 1995, nowU.S. Pat. No. 5,580,889; which is a division of U.S. Ser. No.08/169,902, filed Dec. 20, 1993, now U.S. Pat. No. 5,428,032; which is adivision of U.S. Ser. No. 08/067,642, filed May 25, 1993, now U.S. Pat.No. 5,461,167; which is a division of U.S. Ser. No. 07/832,174, filedFeb. 6, 1992, now U.S. Pat. No. 5,298,507; which is a division of U.S.Ser. No. 07/557,292, filed Jul. 24, 1990, now U.S. Pat. No. 5,204,360;which is a division of U.S. Ser. No. 07/347,836, filed May 4, 1989, nowU.S. Pat. No. 5,001,138; which is a division of U.S. Ser. No.07/068,991, filed Jul. 1, 1987, now U.S. Pat. No. 4,845,106; which is adivision of U.S. Ser. No. 06/821,621, filed Jan. 21, 1986, now U.S. Pat.No. 4,742,060.

The present invention relates to novel heterogyclic compounds, toprocesses for their preparation, to their use as insecticides.

It has already been disclosed that not only certain nitromethylenederivatives have insecticidal function, for instance,1-benzyl-2-nitromethylene tetrahydropyrimidine (see DE-OS 2,514,402),but certain triazolidine derivatives have anti-tumor function againstgastrointestinal tumor (see Japanese Laid-Open Patent Publication196,877/1984).

Furthermore, 1-benzyl-2-nitroiminoimidazolidine has been described inCan. J. Chem., vol. 39, pages 1787-1796.

There have now been found novel heterocyclic compounds of the formula(I):

wherein

n represents 0 or 1,

R¹, R², R⁵ and R⁶ independently represent a hydrogen atom or an alkylgroup, R³ and R⁴ independently represent a hydrogen atom, a hydroxygroup or an alkyl group,

where n represents 1, then R² may form a single bond, together with R⁵,

X represents a sulfur atom, an oxygen atom,

or

wherein

R⁷ represents a hydrogen atom, a halogen atom,

a hydroxy group, an alkoxy group,

a benzyloxy group, an alkyl group which may be substituted by at leastone substituent selected from the class consisting of alkoxy groups,alkylthio groups, a cyano group, halogen atoms, dialkylamino groups andtrialkylsilyl,

an alkenyl group which may be substituted by a halogen atom, an alkynylgroup which may be substituted by a halogen atom, a phenyl group whichmay be substituted by an alkyl group and/or a halogen atom,

a benzyl group which may be substituted by at least one substituentselected from the class consisting of a methyl group, a methoxy group,halogen atoms, halomethyl groups, halomethoxy groups and a nitro group,a formyl group,

an alkenylcarbonyl group, an alkylcarbonyl group which may besubstituted by at least one substituent selected from the classconsisting of alkoxy groups, a phenoxy group, alkylthio groups, andhalogen atoms, a benzoyl group which may be substituted by at least onesubstituent selected from the class consisting of halogen atoms, alkylgroups, halomethyl groups, alkoxy groups, haloalkoxy groups and a nitrogroup, a benzyl-carbonyl group which may be substituted by an alkylgroup and/or a halogen atom, an alkoxycarbonyl group which may besubstituted by a halogen atom, an alkylthiocarbonyl group,

a phenoxycarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of methyl group, amethoxy group, halomethyl group, halomethoxy groups, halogen atoms and anitro group, a phenylthiocarbonyl group which may be substituted by ahalogen atom and/or an alkyl group,

a benzyloxycarbonyl group,

a monoalkyl- or dialkyl-aminocarbonyl group,

a phenylaminocarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of alkyl groups,haloalkyl groups and halogen atoms, a benzoylaminocarbonyl group whichmay be substituted by an alkyl group and/or a halogen atom,

a phenylsulfonylaminocarbonyl group which may be substituted by an alkylgroup and/or a halogen atom, a phenylthio group which may be substitutedby an alkyl group and/or a halogen atom, an alkylsulfonyl group whichmay be substituted by a halogen atom, a phenylsulfonyl group which maybe substituted by at least one substituent selected from the classconsisting of alkyl groups, halogen atoms and a nitro group, analkylcarbonylmethyl group,

a phenacyl group which may be substituted by a halogen atom and/or analkyl group,

an organophosphono group, an organothionophosphono group,

—CH₂—W or —CO—W,

 wherein

W represents a 5 to 6 membered heterocyclic group, containing at leastone hetero atom selected from the class consisting of an oxygen atom, asulfur atom and a nitrogen atom, which may be substituted by at leastone substituent selected from the class consisting of halogen atoms,alkyl groups and haloalkyl groups,

R⁸ represents a hydrogen atom, an alkyl group, an aryl group or a benzylgroup,

Y represents a nitrogen atom or

wherein

R⁹ represents a hydrogen atom, a halogen atom, a hydroxy group, analkoxy group, a benzyloxy group, an alkyl group which may be substitutedby at least one substituent selected from the class consisting ofhalogen atoms, a hydroxy group, alkoxy groups, alkylthio groups, a cyanogroup, mono- or dialkylamino groups, alkylcarbonyl groups,alkoxycarbonyl groups and phenoxycarbonyl groups,

an alkenyl group which may be substituted by a halogen atom, an alkynylgroup, a phenyl group which may be substituted by an alkyl group and/ora halogen atom, an alkylcarbonyl group which may be substituted by ahalogen atom, an alkenylcarbonyl group, a benzoyl group which may besubstituted by at least one substituent select from the class consistingof halogen atoms, alkyl groups and alkoxy groups,

an alkoxycarbonyl group which may be substituted by a halogen atom,

an alkylthiocarbonyl group,

a phenoxycarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of halogen atoms, alkylgroups, alkoxy groups and a nitro group,

a phenylthiocarbonyl group which may be substituted by an alkyl groupand/or a halogen atom, a phenylthiocarbonyl group which may besubstituted by an alkyl group and/or a halogen atom, a benzyloxycarbonylgroup,

a benzoylaminocarbonyl group which may be substituted by an alkyl groupand/or a halogen atom, a phenylsulfonylaminocarbonyl group which may besubstituted by an alkyl group and/or a halogen atom, analkylsulfonylaminocarbonyl group,

an alkylthio group,

an alkylsulfonyl group which may be substituted by a halogen atom,

a phenylthio group which may be substituted by an alkyl group and/or ahalogen atom,

a phenylsulfonyl group which may be substituted by an alkyl group and/ora halogen atom, in addition, R⁹ may form a bis-form of the formula (I),via a methylene group,

R represents a hydrogen atom or an alkyl group, and

Z represents a 5 to 6 membered heterocyclic group containing at leastone hetero atom selected from the class consisting of an oxygen atom, asulfur atom and a nitrogen atom, which may be substituted by at leastone substituent selected from the class consisting of halogen atoms,alkyl groups, haloalkyl groups, a nitro group, a cyano group, alkoxygroups, alkylthio groups, alkylsulfinyl groups, alkylsulfonyl groups,alkenyl groups, haloalkoxy group, haloalkylthio groups, haloalkenylgroups, acylamino groups, haloacylamino groups, alkoxycarbonyl groups,

a thiocyanato group, alkynyl groups, an amino group, alkylamino groups,dialkylamino groups, a carboxy group, a hydroxy group, a mercapto group,cycloalkyl groups, an oxo group,

a thioxo group, haloalkenylthio groups, alkoxyalkyl groups,alkoxycarbonylamino groups,

a carbamoyl group, acyl groups, alkylaminocarbonyl groups,dialkylaminocarbonyl groups, a formyl group, aryl groups optionallysubstituted by a substituent selected from the class consisting ofhalogen atoms, alkyl groups, halogenoalkyl groups, alkoxy groups, anitro group and a cyano group, aryloxy groups optionally substituted bythe substituent as that shown for the above aryl groups, and

aralkyl groups optionally substituted by the same substituent as thatshown for the aryl groups, provided that where R¹, R², R³, R⁴, R⁵ and R⁶represent hydrogen atoms simultaneouly,

X represents

and Y represents

then Z must not stand for the pyridyl group.

In the case of compounds according to the formula (I) having thefollowing formula (Ia):

wherein

n, R¹, R², R³, R⁴, R⁵, R⁶, R, R⁹ and Z have the same meanings as statedabove,

X¹ represents a sulfur atom, a oxygen atom or the following group

R¹⁰ means, in the definition of R⁷, other groups than acyl groupsincluding sulfonyl groups and phosphono groups,

the compounds of the formula (Ia) are obtained when

(a) the compounds of the formula (II)

wherein n, R¹, R², R³, R⁴, R⁵, R₆, R, X¹ and Z have the same meanings asstated above,

are reacted with the compounds of the formula (III)

wherein R′ represents a lower alkyl or a benzyl group, or the two R'smay form a ring, together with two sulfur atoms to which they are bondedand R⁹ has the same meaning as stated above,

if appropriate, in the presence of inert solvents,

(b) the compounds of the above formula (II) are reacted with thecompounds of the formula (IV)

wherein Hal represents a halogen atom and R″ represents a hydrogen atom,a halogen atom or a lower alkyl group,

if appropriate, in the presence of inert solvents and in the presence ofacid acceptors, or

(c) the compounds of the above formula (II) are reacted with thecompounds of the formula (V)

wherein Hal and R″ have the same meanings as stated above,

if appropriate, in the presence of inert solvents and in the presence ofacid acceptors.

In the case of compounds according to the formula (I) having thefollowing formula (Ib):

wherein n, R¹, R², R³, R⁴, R⁵, R⁶, R, X¹ and Z have the same meanings asstated above,

the compounds of the formula (Ib) are obtained when

(d) the compounds of the aforesaid formula (II) are reacted withnitroguanidine of the following formula

if appropriate, in the presence of inert solvents.

In the case of the formula (I) having the following formula (Ic)

wherein n, R¹, R², R³, R⁴, R⁵, R⁶, X, R and Z have the same meanings asstated above,

the compounds of the formula (Ic) are obtained when

(e) the compounds of the formula (VI)

wherein n, R¹, R², R³, R⁴, R⁵, R⁶, X, R and Z have the same meanings asstated above, are reacted with fuming nitric acid,

if appropriate, in the presence of inert solvent.

The compounds of the formula (I) are obtained when

(f) the compounds of the formula (VII)

wherein n, R¹, R², R³, R⁴, R⁵, R⁶, X and Y have the same meanings asstated above,

are reacted with the compounds of the formula (VIII)

wherein

R and Z have the same meaning as stated above,

M represents a halogen atom or

—OSO₂T,

 and

T represents a lower alkyl group, a phenyl group or a tolyl group,

if appropriate, in the presence of inert solvents and in the presence ofacid acceptors.

The novel heterocyclic compounds exhibit powerful insecticidalproperties.

Surprisingly, the heterocyclic compounds according to the inventionexhibit a substantially greater and much more excellent insecticidalaction than the closest known compounds from the aforementioned priorart.

In addition, the heterocyclic compounds according to the invention alsoexhibit a remarkable insecticidal action against harmful insects, inparticular sucking insects typified by insects of Hemiptera such asaphids, plant hoppers and leaf hoppers, which have acquired resistanceto organic phosphate and carbamate type-insecticides caused by long termuse.

Among the novel heterocyclic compounds according to the invention, ofthe formula (I), preferred compounds are those in which

n represents 0 or 1,

R¹, R², R⁵ and R⁶ independently represent a hydrogen atom or an alkylgroup having 1 to 4 carbon atoms, R³ and R⁴ independently represent ahydrogen atom, a hydroxy group or an alkyl group having 1 to 4 carbonatoms,

X represents a sulfur atom, an oxygen atom,

or

R⁷ represents a hydrogen atom, a fluorine atom,

a chlorine atom, a bromine atom, a hydroxy group,

an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, an alkylgroup having 1 to 4 carbon atoms which may be substituted by at leastone member selected from the class consisting of alkoxy groups having 1to 4 carbon atoms, alkylthio groups having 1 to 4 carbon atoms,

a cyano group, a fluorine atom, a chlorine atom, a bromine atom, adimethylamino group and trimethylsilyl,

an alkenyl group having 2 to 3 carbon atoms which may be substituted bya chlorine atom, an alkynyl group having 2 to 3 carbon atoms,

a benzyl group which may be substituted by at least one substituentselected from the class consisting of a methyl group, a methoxy group, afluorine atom, a chlorine atom, a bromine atom and a nitro group, aformyl group, an alkenylcarbonyl group having an alkenyl part with 2 to3 carbon atoms,

an alkyl group having 1 to 5 carbon atoms which may be substituted by atleast one substituent selected from the class consisting of a methoxygroup, a phenoxy group, a fluorine atom, a chlorine atom and a bromineatom, a benzoyl group which may be substituted by at least onesubstituent selected from the class consisting of a fluorine atom, achlorine atom, a bromine atom, a methyl group, a trifluoromethyl group,a methoxy group, a difluoromethoxy group, a trifluoromethoxy group and anitro group,

a benzylcarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of a fluorine atom, achlorine atom and a bromine atom, an alkoxycarbonyl group having analkyl with 1 to 4 carbon atoms which may be substituted by a fluorineatom and/or a chlorine atom, an alkylthiocarbonyl group having an alkylwith 1 to 4 carbon atoms,

a phenoxycarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom and a bromine atom,

a phenylthiocarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom and a bromine atom, a benzyloxycarbonylgroup,

a dimethylaminocarbonyl group, a phenylaminocarbonyl group which may besubstituted by at least one substituent selected from the classconsisting of a methyl group, a fluorine atom, a chlorine atom, and abromine atom,

a benzoylaminocarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom and a bromine atom,

a phenylsulfonylaminocarbonyl group which may be substituted by at leastone substituent selected from the class consisting of a fluorine atom, achlorine atom and a bromine atom, a phenylthio group,

an alkylsulfonyl group which may be substituted by a fluorine atomand/or a chlorine atom,

a phenylsulfonyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom, a bromine atom and a nitro group,

a methylcarbonylmethyl group,

a phenacyl group which may be substituted by a fluorine atom and/or achlorine atom, an organophosphono group, an organothionophosphono group,

—CH₂—W or —CO—W,

W represents a 5 to 6 membered hetercyclic group, containing one or twohetero atoms selected from the class consisting of an oxygen atom,

a sulfur atom and a nitrogen atom, which may be substituted by at leastone substituent selected from the class consisting of a fluorine atom, achlorine atom, a bromine atom and alkyl groups having 1 to 4 carbonatoms,

R⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbonatoms, a phenyl group or a benzyl group,

Y represents a nitrogen atom or

R⁹ represents a hydrogen atom, a fluorine atom,

a chlorine atom, a bromine atom, a hydroxy group,

an alkoxy group having 1 to 4 carbon atoms,

a benzyloxy group, an alkyl group having 1 to 4 carbon atoms which maybe substituted by at least one selected from the class consisting of afluorine atom, a chlorine atom, a hydroxy group, an alkoxy group having1 to 2 carbon atoms, alkylthio groups having 1 to 2 carbon atoms, acyano group,

a dimethylamino group, alkylcarbonyl groups having an alkyl with 1 to 2carbon atoms and alkoxycarbonyl groups having an alkyl with 1 to 2carbon atoms,

an alkenyl group having 2 to 3 carbon atoms,

a phenyl group,

an alkylcarbonyl group having an alkyl with 1 to 4 carbon atoms whichmay be substituted by at least one selected from the class consisting ofa methoxy group, a chlorine atom and a fluorine atom,

an alkenylcarbonyl group having an alkenyl with 2 to 3 carbon atoms,

a benzoyl group which may be substituted by at least one substituentselected from the class consisting of a fluorine atom, a chlorine atom,a bromine atom,

a methoxy group and a methyl group,

an alkoxycarbonyl group which may be substituted by a fluorine atomand/or a chlorine atom,

an alkylthiocarbonyl group having an alkyl with 1 to 4 carbon atoms,

a phenoxycarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of a fluorine atom, achlorine atom, a bromine atom, a methyl group, a methoxy group and anitro group,

a phenylthiocarbonyl group, a benzyloxycarbonyl group,

a benzoylaminocarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom and a bromine atom,

a phenylsulfonylaminocarbonyl group which may be substituted by at leastone substituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom and a bromine atom,

an alkylsulfonylaminocarbonyl group having an alkyl with 1 to 4 carbonatoms,

an alkylthio group having 1 to 4 carbon atoms,

an alkylsulfonyl group which may be substituted by a fluorine atomand/or a chlorine atom,

a phenylthio group which may be substituted by at least one substituentselected foam the class consisting of a methyl group, a fluorine atom, achlorine atom and a bromine atom, or

a phenylsulfonyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom and a bromine atom,

in addition, R⁹ may form a bis-form of the formula (I), via a methylenegroup,

R represents a hydrogen atom or a methyl group, and

Z represents a 5 to 6 membered heterocyclic group, containing one tothree hetero atoms selected from the class consisting of an oxygen atom,a sulfur atom and a nitrogen atom, at least one of which is a nitrogenatom, which may be substituted by at least one substituent selected fromthe class consisting of a fluorine atom, a chlorine atom, a bromineatom, alkyl groups having 1 to 4 carbon atoms which may be substitutedby a fluorine atom and/or a chlorine atom,

a nitro group, a cyano group,

alkylsulfinyl groups having 1 to 4 carbon atoms, alkylsulfonyl groupshaving 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atomswhich may be substituted by a fluorine atom and/or a chlorine atom,

alkylthio groups having 1 to 4 carbon atoms which may be substituted bya fluorine atom and/or a chlorine atom,

alkenyl groups having 2 to 3 carbon atoms which may be substituted by achlorine atom,

an acetamide group which may be substituted by a fluorine atom and/or achlorine atom, alkoxycarbonyl groups having an alkyl with 1 to 4 carbonatoms, a thiocyanato group, alkynyl groups having 2 to 4 carbon atoms,an amino group, a methylamino group,

a dimethylamino group, an acetyl group,

a formyl group, a carboxy group, a hydroxy group,

a mercapto group, cycloalkyl groups having 3 to 7 carbon atoms, an oxogroup, a thioxo group, alkenylthio groups substituted by a fluorineatom, a chlorine atom and/or a bromine atom, alkoxyalkyl groups having 2to 4 carbon atoms in total, alkylaminocarbonyl groups having an alkylwith 1 to 2 carbon atoms,

dialkylaminocarbonyl groups having an alkyl with 1 to 2 carbon atoms,

a phenyl group, a phenoxy group and a benzyl group, provided that whereR¹, R², R³, R⁴, R⁵ and R⁶ represent hydrogen atoms simultaneously,

X represents

and

Y represents

then Z must not stand for the pyridyl group.

Very particularly preferred heterocyclic compounds of the formula (I)are those in which

n represents 0 or 1,

R¹, R², R⁵ and R⁶ independently represent a hydrogen atom or a methylgroup,

R³and R⁴ independently represent a hydrogen atom or a methyl group,

X represents a sulfur atom, an oxygen atom or the following groups

or

R⁷ represents a hydrogen atom, an alkyl group which may be substitutedby at least one substituent selected from the class consisting of amethoxy group, an ethoxy group, a methylthio group, an ethylthio group,a cyano group, a fluorine atom, a chlorine atom and a trimethylsilylgroup,

an allyl group which may be substituted by a chlorine atom, a propargylgroup

a benzyl group which may be substituted by a methyl group and/or achlorine atom,

a formyl group, a vinylcarbonyl group,

an alkylcarbonyl group having an alkyl with 1 to 3 carbon atoms whichmay be substituted by at least one substituent selected from the classconsisting of methoxy group, a phenoxy group and a chlorine atom, abenzoyl group which may be substituted by at least one substituentselected from the class consisting of chlorine atom, a bromine atom, amethyl group,

a trifluoromethyl group, a methoxy group and a nitro group,

a benzylcarbonyl group which may be substituted by a chlorine atom,

an alkoxycarbonyl group having an alkyl with 1 to 2 carbon atoms whichmay be substituted by a fluorine atom and/or a chlorine atom,

an alkylthiocarbonyl group having an alkyl with 1 to 2 carbon atoms,

a phenoxycarbonyl group which may be substituted by a methyl groupand/or a chlorine atom,

a phenylthiocarbonyl group which may be substituted by a chlorine atom,

a benzyloxycarbonyl group, a dimethylaminocarbonyl group, aphenylaminocarbonyl group,

a benzoylaminocarbonyl group,

a phenylsulfonylaminocarbonyl group which may be substituted by a methylgroup and/or a chlorine atom,

a phenylthio group,

a methylsulphonyl group which may be substituted by chlorine atom,

a phenylsulphonyl group which may be substituted by a methyl group,

a methylcarbonylmethyl group,

a phenacyl group which may be substituted by a chlorine atom,

O,O-diethylthionophosphono group,

O-ethyl-S-n-propylthiolophosphono group,

—CH₂—W or —CO—W wherein

W represents a 5 to 6 membered heterocyclic group, containing one or twohetero atoms selected from the class consisting of an oxygen atom, asulfur atom and a nitrogen atom, which may be substituted by a fluorineatom, a chlorine atom, a bromine atom and a methyl group,

R⁸ represents a hydrogen atom, a methyl group, a phenyl group or abenzyl group,

Y represents a nitrogen atom or

R⁹ represents a hydrogen atom, a chlorine atom,

a bromine atom, a hydroxy group, a methoxy group,

a benzyloxy group, an alkyl group which may be substituted by at leastone substituent selected from the class consisting of a fluorine atom, achlorine atom,

a hydroxy group, a methoxy group, a cyano group, a dimethylamino group,an acetyl group and a methoxycarbonyl group,

an allyl group, a phenyl group, an acetyl group which may be substitutedby a chlorine atom, a vinylcarbonyl group,

an allylcarbonyl group, a benzoyl group,

an alkoxycarbonyl group having an alkyl with 1 to 2 carbon atoms whichmay be substituted by a fluorine atom,

n-butylthiocarbonyl group, a phenoxycarbonyl group which may besubstituted by a chlorine atom and/or a methyl group, aphenylthiocarbonyl group, a benzyloxycarbonyl group, abenzoylaminocarbonyl group which may be substituted by a chlorine atom,a phenylsulfonylaminocarbonyl group which may be substituted by a methylgroup,

a methylsulfonylaminocarbonyl group,

a propylthio group, a methylsulphonyl group which may be substituted bya fluorine atom and/or a chlorine atom, a phenylthio group which may besubstituted by a chlorine atom, or a phenylsulphonyl group,

in addition, R⁹ may form a bis-form of the formula (I), via a methylenegroup, R represents a hydrogen atom or a methyl group, and

z represents a 5 to 6 membered heterocyclic group, containing one tothree hetero atoms selected from the class consisting of an oxygen atom,a sulfur atom and a nitrogen atom, at least one of which is a nitrogenatom, which may be substituted by at least one substituent selected fromthe class consisting of a fluorine atom, chlorine atom, a bromine atom,a methyl group. fluoroalkyl groups having 1 to 2 carbon atoms,

a methoxy group, a methylthio group, a methylsulphinyl group, amethylsulphonyl group, a nitro group, a cyano group, a trifluoromethoxygroup, a trifluoromethylthio group, an allyl group, an acetamide group,a methoxycarbonyl group,

an acetyl group, a formyl group and a carboxyl group, provided thatwhere R¹, R², R³, R⁴, R⁵ and R⁶ represent hydrogen atoms simultaneously,

X represents

and Y represents

then

Z must not stand for the pyridyl group.

Specifically, the following compounds may be mentioned:

3-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazine,

3-(2-chloro-5-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazine,

3-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazine,

3-(2-bromo-5-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-(2-methyl-5-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-(2-methyl-5-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazine,

3-(2-ethyl-5-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-(2-trifluoromethyl-5-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazine,

3-(3-pyridylmethyl)-2-(nitromethylene)thiazolidine,

3-(3-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazine,

3-(2-trifluoromethyl-5-pyridylmethyl)-2-(nitromethylene)thiazolidine.

1-(5-pyrazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(5-chloro-1-methyl-3-pyrazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(1-methyl-4-pyrazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(1-methyl-4-pyrazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(3-trifluoromethyl-5-isoxazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(3-methyl-5-isoxazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(3-methyl-5-isoxazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(5-isoxazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-methyl-5-thiazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-thiazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(2-trifluoromethyl-5-thiazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(1,2,5-thiadiazol-3-ylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(1,2,3-thiadiazol-5-ylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(2-methyl-5-thiazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(2-chloro-5-thiazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(1,2,5-thiadiazol-3-ylmethyl)-2-(nitromethylene)imidazolidine,

1-(5-thiazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(5-pyrimidinylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-methyl-5-pyrimidinylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-pyrazinylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-methyl-5-pyrazinylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-pyrimidinylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(2-chloro-5-pyrimidinylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-fluoro-5-pyrimidinylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-trifluoromethyl-5-pyrimidinylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-pyrazinylmethyl)-2-(nitromethylene)imidazolidine,

1-[1-(2-fluoro-5-pyrimidinyl)ethyl]-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-pyridylmethyl)-2-(nitroimino)tetrahydropyrimidine,

1-(2-chloro-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-trifluoromethyl-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-trifluoromethyl-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-fluoro-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-bromo-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-methyl-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-methoxy-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)pyrolidine,

1-(2-chloro-5-thiazolylmethyl)-2-(nitroimino)tetrahydropyrimidine,

1-(2-chloro-5-pyrimidinylmethyl)-2-(nitroimino)imidazolidene,

1-(2-chloro-5-pyridylmethyl)-4-methyl-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-pyridylmethyl)-3-(3-pyridylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-pyridylmethyl)-2-(bromonitromethylene)imidazolidine,

1-(2-chloro-5-pyridylmethyl)-2-(1-nitro-2-oxopentylidene)imidazolidine,

ethyl nitro[3-(2-chloro-5-pyridylmethyl)thiazolidin-2-ylidene]acetate,

1-acetyl-3-(2-chloro-5-pyridylmethyl)-2-(nitroimino)imidazolidine, and

N-phenylsulfonyl-nitro[1-(2-chloro-5-pyridylmethyl)imidazolidin-2-ylidene]acetamide.

If, in the process (a), for example,N-(1-methyl-4-pyrazolymethyl)trimethylene diamine and1-nitro-2,2-bis(methylthio) ethylene are used as starting materials, thecourse of the reaction can be represented by the following equation:

If, in the process (b), for example,2-(2-methyl-5-pyrazinylmethylamino)ethanethiol and2,2-dichloronitroethylene are used as starting materials, the course ofthe reaction can be represented by the following equation:

If, in the process (c), for example,2-(2-chloro-5-thiazolylmethylamino)ethanethiol and1,2,2,2-tetrachloro-1-nitroethane are used as starting materials, thecourse of the reaction can be represented by the following equation:

If, in the process (d), for example,N-(2-chloro-5-pyridylmethyl)trimethylenediamine and nitroguanidine areused as starting materials, the course of the reaction can berepresented by the following equation:

If, in the process (e), for example,1-(2-chloro-5-pyridylmethyl)-2-iminoimidazolidine and fuming nitric acidare used as starting materials, the course of the reaction can berepresented by the following equation:

If, in the process (f), for example, 2-nitromethylenethiazolidine and2-chloro-5-pyridylmethylchloride are used as starting materials, thecourse of the reaction can be represented by the following equation:

The formula (II) provides a general definition of the compounds requiredas a staring material in the process a), based on aforesaid eachdefinition of n, R¹, R², R³, R⁴, R⁵, R⁶, R, Z and X¹.

In the formula (II), n, R¹, R², R³, R⁴, R⁵, R⁶, R, Z and X¹ preferablyhave the meanings already given above.

The compounds of the formula (II) usable according to the inventioninclude both known and novel ones.

The known examples have already been described in, for instance,Japanese Patent Application Nos. 26,020/1984, 72,966/1954 and132,943/1984 Z. Anorg. Allgem. Chem., Vol. 312, pages 282-286, Khim.Geterotsikl. Soedin., 1974, No. 1, pages 122-123, Metody Poluch. Khim.Reactivon Prep., No. 17, pages 172-173, Issled. Obl. Geterotsikl.Soedin., 1971, pages 39-44, U.S. Pat. No. 4,018,931, Arch. Pharm., 1982,Vol. 315, pages 212-221, Metody Poluch. Khim. Reactivon Prep., 1967,pages 133-134, and Zh. Obshch Khim., Vol. 33, pages 1130-1135.

As examples, there may be mentioned, the following:

N-(2-chloro-5-pyridylmethyl)2-aminoethanethiol,

N-(2-chloro-5-pyridylmethyl)3-aminopropanethiol,

N-(2-bromo-5-pyridylmethyl)2-aminoethanethiol,

N-(2-bromo-5-pyridylmethyl)3-aminopropanethiol,

N-(2-fluoro-5-pyridylmethyl)2-aminoethanethiol,

N-(2-fluoro-5-pyridylmethyl)3-aminopropanethiol,

N-[1-(2-chloro-5-pyridyl)ethyl]2-aminoethanethiol,

N-(2,3-dichloro-5-pyridylmethyl)2-aminoethanethiol,

N-(3-chloro-2-fluoro-5-pyridylmethyl)2-aminoethanethiol,

N-(2-chloro-4-pyridylmethyl)2-aminoethanethiol,

N-(3-chloro-2-pyridylmethyl)2-aminoethanethiol,

N-(5-chloro-2-pyridylmethyl)3-aminopropanethiol,

N-(3,5-dichloro-2-pyridylmethyl)2-aminoethanethiol,

N-(5-fluoro-2-pyridylmethyl)3-aminopropanethiol,

N-(6-bromo-2-pyridylmethyl)2-aminoethanethiol,

N-(2-chloro-3-pyridylmethyl)3-aminopropanethiol,

N-(5-chloro-3-pyridylmethyl)3-aminopropanethiol,

N-(5-bromo-3-pyridylmethyl)2-aminoethanethiol,

N-(5-fluoro-3-pyridylmethyl)2-aminoethanethiol,

N-[1-(2-fluoro-5-pyridyl)ethyl]2-aminoethanethiol,

N-(2,4-dichloro-5-pyridylmethyl)3-aminopropanethiol,

N-(2,4-dibromo-5-pyridylmethyl)2-aminoethanethiol,

N-(2,6-difluoro-4-pyridylmethyl)2-aminoethanethiol,

N-(2-fluoro-4-pyridylmethyl)3-aminopropanethiol,

N-(2,6-dibromo-4-pyridylmethyl)2-aminoethanethiol,

N-(3-bromo-2-fluoro-5-pyridylmethyl)2-aminoethanethiol,

N-(2-chloro-3-fluoro-5-pyridylmethyl)2-aminoethanethiol,

N-[1-(2-chloro-5-pyridyl)propyl]2-aminoethanethiol,

N-(3-pyridylmethyl)2-aminoethanethiol,

N-(3-pyridylmethyl)3-aminopropanethiol,

N-(4-pyridylmethyl)2-aminoethanethiol,

N-(4-pyridylmethyl)3-aminopropanethiol,

N-(2-methyl-5-pyridylmethyl)2aminoethanethiol,

N-(2-methyl-5-pyridylmethyl)3-aminopropanethiol,

N-(2-ethyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-allyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-propargyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-methoxy-5-pyridylmethyl)3-aminopropanethiol,

N-(2-methylthio-5-pyridylmethyl)2-aminopropanethiol,

N-(2-methylsulfonyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-chloro-3-methyl-5-pyridylmethyl)2-aminoethanethiol,

N-[1-(3-pyridyl)ethyl]3-aminopropanethiol,

N-(2-trifluoromethyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-trifluoromethyl-5-pyridylmethyl)3-aminopropanethiol,

N-(2-nitro-5-pyridylmethyl)2-aminoethanethiol,

N-(2-nitro-5-pyridylmethyl)3-aminopropanethiol,

N-(2-cyano-5-pyridylmethyl)2-aminoethanethiol,

N-(2-cyano-5-pyridylmethyl)3-aminopropanethiol,

N- (2-methylsulfinyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-phenyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-benzyl-5-pyridylmethyl)2aminoethanethiol,

N-(2-phenoxy-5-pyridylmethyl)3-aminopropanethiol,

N-(2-trichloromethyl-5-pyridylmethyl)2-aminoethanethiol,

N-[2-(2-ethoxyethyl)-5-pyridylmethyl]3-aminopropanethiol,

N-(2-methoxymethyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-difluoromethoxy-5-pyridylmethyl)2-aminoethanethiol,

N-(2-trifluoromethoxy-5-pyridylmethyl)2-aminoethanethiol,

N-[2-(2,2,2-trifluoroethoxy)-5-pyridylmethyl]2-aminoethanethiol,

N-(2-chlorodifluoromethylthio-5-pyridylmethyl)3-aminopropanethiol,

N-(2-trifluoromethylthio-5-pyridylmethyl)2-aminoethanethiol,

N-(2-difluoromethyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-trifluoromethylsulfonyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-trifluoromethylsulfinyl-5-pyridylmethyl)2-aminoethanethiol,

N-[2-(2,2-dichlorovinyl)-5-pyridylmethyl)2-aminoethanethiol,

N-(4-pyrimidinylmethyl)ethylenediamine,

N-(2-methyl-4-pyrimidinylmethyl)ethylenediamine,

N-(2-methyl-6-oxo-1H,6H-dihydropyrimidin-4-yl-methyl)trimethylenediamine,

N-(5-pyrimidinylmethyl)ethylenediamine,

N-(2-methyl-5-pyrimidinylmethyl)ethylenediamine,

N-(2-dimethylamino-5-pyrimidinylmethyl)ethylenediamine,

N-(2-dimethylamino-5-pyrimidinylmethyl)trimethylenediamine,

N-′2,4,6-trichloro-5-pyrimidinylmethyl)ethylenediamine,

N-(pyrazinylmethyl)ethylenediamine,

N-[1-(pyrazinyl)ethyl]ethylenediamine,

N-(2-methyl-5-pyrazinylmethyl)ethylenediamine,

N-(3-pyridazinylmethyl)ethylenediamine,

N-(2-chloro-4-pyrimidinylmethyl)ethylenediamine,

N-(4-chloro-6-pyrimidinylmethyl)ethylenediamine,

N-(4-methyl-6-pyrimidinylmethyl)trimethylenediamine,

N-(2-fluoro-5-pyrimidinylmethyl)ethylenediamine,

N-[1-(2-fluoro-5-pyrimidinyl)ethyl]ethylenediamine,

N-(2-chloro-5-pyrimidinylmethyl)ethylenediamine,

N-(2-chloro-5-pyrimidinylmethyl)trimethylenediamine,

N-(2-isopropyl-5-pyrimidinylmethyl)ethylenediamine,

N-(2-chlorodifluoromethyl-5-pyridinylmethyl)ethylenediamine,

N-(2-trifluoromethyl-5-pyrimidinylmethyl)ethylenediamine,

N-(2-bromodifluoromethyl-5-pyrimidinylmethyl)ethylenediamine,

N-(2-methoxy-5-pyrimidinylmethyl)ethylenediamine,

N-(2-difluoromethoxy-5-pyrimidinylmethyl)ethylenediamine,

N-(2-trifluoromethoxy-5-pyrimidinylmethyl)ethylenediamine,

N-[2(2,2,2trifluoroethoxy)-5-pyrimidinylmethyl]-trimethylenediamine,

N-(2methylthio-5-pyrimidinylmethyl)ethylenediamine,

N-(2-ethylthio-5-pyrimidinylmethyl)ethylenediamine,

N-(2-difluoroethylthio-5-pyrimidinylmethyl)ethylenediamine,

N-(2-trifluoromethylthio-5-pyrimidinylmethyl)ethylenediamine,

N-[2-(2,2,2-trifluoroethylthio)-5-pyrimidinylmethyl)-ethylenediamine,

N-(2-nitro-5-pyrazinylmethyl)ethylenediamine,

N-(2-cyano-5-pyrazinylmethyl)trimethylenediamine,

N-(2-chloro-5-pyrazinylmethyl)ethylenediamine,

N-(2-trifluoromethyl-5-pyrazinylmethyl)ethylenediamine,

N-(3-fluoro-6-pyridazinylmethyl)ethylenediamine,

N-(3-methyl-6-pyridazinylmethyl)trimethylenediamine,

N-(4-pyridazinylmethyl)ethylenediamine,

N-(3-chloro-6-pyridazinylmethyl)ethylenediamine,

N-(4-pyridazinylmethyl)trimethylenediamine,

N-(3-trifluoromethyl-6-pyridazinylmethyl)ethylenediamine,

N-(1,3,5-triazin-2-ylmethyl)ethylenediamine,

N-(3-chloro-1,2,4-triazin-6-ylmethyl)ethylenediamine,

N-(3,5-dichloro-1,2,4-triazin-6-ylmethyl)ethylenediamine,

N-(3-chloro-1,2,4,5-tetrazin-6-ylmethyl)ethylenediamine,

N-(3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(furfuryl)-ethylene(or -trimethylene)diamine,

N-(5-methylfurfuryl)-ethylene(or -trimethylene)diamine,

N-(2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-5-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(tetrahydrofurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-methyltetrahydrofurfuryl)ethylene(or -trimethylene)diamine,

N-(3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-2-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-bromo-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-cyanofurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-trifluoromethylthio-2-thienylmethyl)-ethylene(or-trimethylene)diamine,

N-[1-(2-thienyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(5-methyl-3-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-5-isoxazolylmethyl)-ethylene (or -trimethylene)diamine,

N-(3-trifluoromethyl-5-isoxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-chloro-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-isothiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(1-methyl-4-pyrazolyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(1-ethyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-isopropyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-allyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-tert-butyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2,2,2-trifluoroethyl)-5-pyrazolylmethyl]ethylene (or-trimethylene)diamine,

N-(3-methyl-5-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-chloro-2-methyl-5-pyrazolylmethyl)-ethylene (or-trimethylene)diamine,

N-(2,3,5-trimethyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-5-thiazolylmethyl)-ethylene (or -trimethylene)diamine,

N-(2-chloro-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethyl-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-bromo-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,4-dichloro-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-2-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,2,4-triazol-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-1,2,4-triazol-3-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,2,5-thiadiazol-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,2,3-thiadiazol-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-1,2,4-oxadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(1,3-dioxolan-2-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,2-dimethyl-1,3-dioxolan-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methyl-2-oxazolin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethyl-2-oxazolin-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-ethyl-2-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-3-thienyl)-ethylene(or -trimethylene)diamine,

N-(1-ethyl-2-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-3-thienyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,5-dimethyl-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,5-dimethyl-3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,5-dimethyl-3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-fluoro-3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-chlorofurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-chlorofurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-chloro-3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-chloro-3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-chloro-1-methyl-3-pyrrolylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-bromo-3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-nitrofufuryl)-ethylene(or -trimethylene)diamine,

N-(4-nitro-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-nitro-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-5-nitro-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-cyano-3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-cyano-3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-cyano-1-methyl-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-trifluoromethylfurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-difluoromethylfurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-trifluoromethyl-3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-5-trifluoromethyl-3-pyrrolylmethyl)ethylene(or-trimethylene)diamine,

N-(5-methoxy-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methylthiofurfuryl)-ethylene(or -trimethylene)diamine,

N-(2,5-dimethylthio-3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-trifluoromethylthiofurfuryl)-ethylene(or -trimethylene)diamine,

N-[5-(2,2-dichlorovinyl)-2-thienylmethyl]-ethylene(or-trimethylene)diamine,

N-(5-ethoxycarbonylfurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-formyl-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-isoxazlylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-isoxazolylmethyl)-ethylne(or -trimethylene)diamine,

N-(3-ethyl-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-isopropyl-5-isoxazolylmethyl)-ethylne(or -trimethylene)diamine,

N-(3-fluoro-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-bromo-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-hydroxy-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-nitro-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-cyano-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-difluoromethyl-5-isoxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-chloromethyl-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methoxymethyl-5-isoxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-isopropoxymethyl-5-isoxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-trichloromethyl-5-isoxazolylmethyl)-ethylene-(or-trimethylene)diamine,

N-(3-methoxy-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-trifluoromethoxy-5-isoxazolylmethyl)-ethylene-(or-trimethylene)diamine,

N-(2,5-dimethyl-4-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-isothiazolylmethylene)-ethylene(or -trimethylene)diamine,

N-(4-isothiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(4-pyrazolyl)ethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-3-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-5-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-propyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2,2,2-trifluoroethyl)-3-pyrazolylmethyl]-ethylene(or-trimethylene)diamine,

N-(5-chloro-1-ethyl-3-pyrazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-chloro-1-isopropyl-3-pyrazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-chloro-1-methyl-3-pyrazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-trifluoromethyl-3-pyrazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(1-methyl-5-trifluoromethyl-3-pyrazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(1-methyl-3-trifluoromethyl-5-pyrazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(4-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-4-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethyl-5-oxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methylthio-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethoxy-5-oxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2,4-dimethyl-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-ethoxycarbonyl-2-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(5-thiazolyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(2-methyl-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2-methyl-5-thiazolyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(2-ethyl-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-isopropyl-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2-chloro-5-thiazolylmethyl)ethyl]-ethylene(or-trimethylene)diamine,

N-(2-nitro-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-nitro-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-cyano-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-cyano-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylthio-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-mercapto-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylthio-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-difluoromethylthio-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-trifluoromethylthio-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-chlorodifluoromethylthio-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-[2-(2,2,2-trifluoromethylthio)-5-thiazolylmethyl]-ethylene(or-trimethylene)diamine,

N-{2-[2-(2,3,3-trichloro)propenylthio]-5-thiazolylmethyl}-ethylene(or-trimethylene)diamine,

N-(2-thiocyanato-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-amino-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-acetamino-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methoxy-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methoxy-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethoxy-5-thiazolylmethyl)-ethylene-(or-trimethylene)diamine,

N-(2-difluoromethoxy-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-chloromethyl-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-difluoromethyl-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-trifluoromethyl-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-[2-(1,1,2,2-tetrafluoroethyl)-5-thiazolylmethyl]-ethylene(or-trimethylene)diamine,

N-(2-cyclopropyl-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-imidazolylmethyl)-ethylene or -trimethylene)diamine,

N-(1-methyl-5-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-flouro-4-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-4-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-nitro-2-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-trifluoromethylthio-4-imidazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(1,2-dimethyl-4-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-2-trifluoromethyl-4-imidazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(1-methyl-1,2,3-triazol-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-[(1-methyl-1,2,3-triazol-4-yl)ethyl]-ethylene(or-trimethylene)diamine,

N-(3-methyl-1,2,4-triazol-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-trifluoromethyl-1,2,4-triazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(1,2,4-oxadiazol-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,3,4-oxadiazol-2-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,2,3-oxadiazol-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-trifluoromethyl-1,2,4-oxadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methyl-1,3,4-oxadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-trifluoromethyl-1,3,4-oxadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-[2-(2,2,2-trifluoroethyl)-1,3,4-oxadiazol-5-ylmethyl]-ethylene(or-trimethylene)diamine,

N-(1,2,4-thiadiazol-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,2,3-thiadiazol-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(1,2,3-thiadiazol-5-yl)ethyl]-ethylene(or -trimethylene)diamine,

N-(1,3,4-thiadiazol-2-yl)-ethylene(or -trimethylene)diamine,

N-[1-(1,3,4-thiadiazol-2-yl)ethyl]-ethylene(or -trimethylene)diamine,

N-(1,2,5-thiadiazol-3-ylmethyl)ethylene(or -trimethylene)diamine,

N-(3-methyl-1,2,4-thiadiazol-5-yl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-1,2,3-thiadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methyl-1,3,4-thiadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-trifluoromethyl-1,3,4-thiadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-fluoro-1,3,4-thiadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-chloro-1,3,4-thiadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-chloro-1,2,5-thiadiazol-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-[1-(3-tetrahydrofuryl)ethyl]-ethylene(or -trimethylene)diamine,

N-(3-tetrahydrothienylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(3-tetrahydrothienyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(1-methyl-3-pyrrolidinylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,3-oxathiolan-2-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,3-dioxolan-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,3-oxathiolan-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,3-dithiolan-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(thiazolidin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-1,3-dioxolan-2-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-1,3-oxathiolan-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-chloromethyl-1,3-dioxolan-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-trifluoromethyl-1,3-dioxolan-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-oxo-1,3-dioxolan-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-formyl-thiazolidin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-acetyl-thiazolidin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,5-dihydrothiophen-2-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,1-dioxo-2,5-dihydrothiophen-3-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-isoxazolin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-2-isoxazolin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-trifluoromethyl-2-isoxazolin-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-[3-(2,2,2-trifluoromethyl)-2-isoxazolin-5-ylmethyl]-ethylene(or-trimethylene)diamine,

N-(2,4-dimethyl-2-oxazolin-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methyl-2-thiazolin-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-oxazolidinon-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-2-oxo-1,3-oxazolan-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methylamino-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoroacetamide-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-methyl-2-thioxo-thiazolidin-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-chloro-1,2,4-oxadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-carboxy-2-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-dimethylamino-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-phenoxyfurfuryl)-ethylene(or -trimethylene)diamine,

N-(1-phenyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-benzyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-phenyl-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-benzyl-2-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylsulfinyl-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methylsulfonyl-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methylthio-1,3,4-thiadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methylsulfonyl-1,3,4-thiadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-dimethylamino-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-carbamoyl-2-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methylaminocarbonyl-2-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-dimethylaminocarbonyl-2-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(3-pyridyl)ethyl]-ethylene(or -trimethylene)diamine,

N-[1-(3-pyridyl)propyl]-ethylene(or -trimethylene)diamine,

N-[2-methyl-1-(3-pyridyl)propyl]-ethylene(or -trimethylene)diamine,

N-(4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-chloro-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2-chloro-5-pyridyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(2-nitro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-cyano-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-amino-5-pyridylmethyl)-ethylene or -trimethylene)diamine,

N-(2-acetamido-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-dimethylamino-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-ethoxycarbonyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-acetyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-3-methyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-difluoromethyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-trifluoromethyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-bromodifluoromethyl-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-chlorodifluoromethyl-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

N-(trichloromethyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[2-(2-chloroethyl)-5-pyridylmethyl]-ethylene(or -trimethylene)diamine,

N-[2-(2-fluoroethyl)-5-pyridylmethyl]-ethylene(or -trimethylene)diamine,

N-[2-(2,2,2-trifluoroethyl)-5-pyridylmethyl]-ethylene(or-trimethylene)diamine,

N-(2-difluoroethoxy-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethoxy-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

N-[2-(2,2,2-trifluoroethoxy)-5-pyridylmethyl]-ethylene(or-trimethylene)diamine,

N-[2-(trifluoromethylthio)-5-pyridylmethyl]-ethylene(or-trimethylene)diamine,

N-(2-formyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chlorodifluoromethylthio-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

N-[2-(2,2-dichlorovinyl)-5-pyridylmethyl]-ethylene(or-trimethylene)diamine,

N-(5-trifluoromethyl2pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(6-methyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-ethyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-butyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(4,6-dimethyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-chloro-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(3,5-dichloro-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-fluoro-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(6-bromo-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[2-(5-ethyl-2-pyridyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(6-chloro-4-methyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-chloro-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-bromo-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-bromo-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-fluoro-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2-fluoro-5-pyridyl)ethyl]-ethylene(or -trimethylene)diamine,

N-[2-methyl-1-(2-fluoro-5-pyridyl)propyl]-ethylene(or-trimethylene)diamine,

N-(2-chloro-6-methyl-3-pyridylmethyl)-ethylene(or -trimethyleneldiamine,

N-(2,4-dichloro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,6-dichloro-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,4-dibromo-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,4-difluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methoxy-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methoxy-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-ethoxy-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-isopropoxy-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylthio-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-2-methylthio-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-ethylthio-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylsulfinyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylsulfonyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-chloro-2-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(6-chloro-2-methyl-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-4-methyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-allyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-propargyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,3-dichloro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[2-(1-propenyl)-5-pyridylmethyl]-ethylene(or -trimethylene)diamine,

N-(2-chloro-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,6-dichloro-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2-chloro-4-pyridyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(2-chloro-6-methyl-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,6-dimethyl-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-bromo-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,6-dibromo-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,6-dichloro-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-chloro-2-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-bromo-2-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-3-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-chloro-2-methylthio-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

2-amino-1-(4-pyridylmethylamino)propane,

2-amino-2-methyl-(3-pyridylmethylamino)propane,

N-(4-pyridylmethyl)-2,2-dimethyltrimethylenediamine,

2-amino-1-(2-chloro-5-pyridylmethylamino)propane,

N-(2-chloro-5-pyridylmethyl)-2-methyltrimethylene-diamine,

N-(3-pyridylmethyl)-N′-methylethylenediamine,

N-(2-chloro-5-pyridylmethyl)-N′-methylethylene(or -trimethylene)diamine,

N-(2-fluoro-5-pyridylmethyl)-N′-isopropylethylenediamine,

N-(2-chloro-5-pyridylmethyl)-N′-benzylethylenediamine,

N-(2-chloro-5-pyridylmethyl)-N′-(3-pyridylmethyl)ethylenediamine,

N-(2-chloro-5-pyridylmethyl)-N′-(1-methyl-4-pyrazolylmethyl)ethylenediamine,

2-methyl-2-(2-methyl-5-pyridylmethylamino)ethanethiol,

1-methyl-2-(2-chloro-5-pyridylmethylamino)ethanethiol,

2-(4-pyridylmethylamino)ethanol,

2-(3-pyridylmethylamino)ethanol,

3-(2-methyl-3-pyridylmethyl)propanol,

2-(2-methyl-5-pyridylmethyl)ethanol,

2-(2-chloro-5-pyridylmethyl)ethanol,

3-(2-trifluoromethyl-5-pyridylmethyl)propanol,

N-(1-methyl-4-pyrazolylmethyl)-2,2-dimethyltrimethylenediamine,

N,N′-bis-(5-methyl-2-furfuryl)ethylenediamine,

N-(3-methyl-5-isoxazolylmethyl)-N′-(1-methyl-4-pyrazolylmethyl)ethylene(or-trimethylene)diamine,

2-(3-methyl-5-isoxazolylmethylamino)ethanethiol,

3-(1-isopropyl-4-pyrazolylmethylamino)propanethiol,

2-(1,2,5-thiadiazol-3-ylmethylamino)ethanethiol,

2-(2-trifluoromethyl-5-thiazolylmethylamino)ethanethiol,

2-(3-methyl-5-isoxazolylmethylamino)ethanol,

2-(4-isothiazolylmethylamino)ethanol,

2-(5-oxazolylmethylamino)ethanol,

2-(3-trifluoromethyl-5-isoxazolylmethylamino)ethanol,

2-(5-pyrimidinylmethylamino)ethanethiol,

2-(3-trifluoromethyl-6-pyridazinylmethylamino)ethanethiol,

2-(2-methyl-5-pyrazinylmethylamino)ethanethiol,

2-(3-pyrazinylmethylamino)ethanol,

2-(3-chloro-6-pyridazinylmethylamino)ethanol,

2-amino-1-(2-pyradinylmethyl)aminopropane,

N-(5-pyrimidinylmethyl)-N′-(1-methyl-4-pyrazolylmethyl)ethylenediamine,and

N-(3-chloro-6-pyridazinylmethyl)-N′-methyethylenediamine.

As aforesaid, the formula (II) includes novel compounds.

In the case of the formula (II) having the following formula (IIa):

wherein n, R¹, R², R³, R⁴, R⁵, R⁶, R and Z have the same meanings asstated above,

x² represents an oxygen atom or

R¹⁰ has the same meanings as stated above,

the compounds of the formula (IIa) can be obtained when

(g) the compounds of the aforesaid formula (VIII) are reacted with thecompounds of the formula (IX)

wherein n, R¹, R², R³, R⁴, R⁵, R⁶ and X² have the same meanings asstated above,

if appropriate, in the presence of inert solvents and in the presence ofacid acceptors.

If, in the process (g), for example, pyrazinylmethyl chloride andethylenediamine are used as starting materials, the course of thereaction can be represented by the following equation:

The compounds of the formula (II) can be obtained when

(h) the compounds of the formula (X)

wherein Z and R have the same meanings as stated above,

are reacted with the compounds of the formula (XI)

wherein R¹, R², R³, R⁴, R⁵, R⁶ and X¹ have the same meanings as statedabove,

and the resulting products are reduced,

if appropriate, in the presence of inert solvents.

If, in the process (h), for example, 6-chloronicotinealdehyde and3-aminopropanethiol are used as starting materials, the course of thereaction can be represented by the following equation:

In addition, if, in the process (h), for example,5-pyrimidinecarbaldehyde and ethylenediamine are used as the startingmaterials, the course of the reaction can be represented by thefollowing equation:

The compounds of the formula (VIII), in the process (g), are the same asthe starting materials in the process (f), as mentioned hereinafter.

The compounds of the formula (IX) which include both known and novelones, can be easily produced by known processes.

As examples of the formula (IX), there may be mentioned:

ethylenediamine, and

trimethylenediamine. (see German Offenlegungsschrift 2,732,660 or FrenchPatent No. 1,499,785)

There may also be mentioned 2-aminoethanol and 3-aminopropanole whichare well known compounds in organic chemistry.

In addition, N-benzyl-ethylene(or trimethylene) diamines [see JapaneseLaid-Open Patent Application No. 78,971/1985, Germs Offenlegungsschrift2,514,402, German Offenlegungsschrift 2,732,660 and Japanese PatentApplication No. 68,551/1985] and N-substituted alkyl-ethylene(ortrimethylene)diamines which correspond to ethylenediamines ortrimethylenediamines in the aforesaid formula (II) also included asexamples of the formula (IX).

In the practice of process (g), the desired compounds of the formula(II) can be easily obtained by reacting the compounds of formula (VII)with the compounds of formula (IX) in inert solvents such as illustratedin process (a) to be described in detail hereinbelow.

The process (g) can be easily carried out by using more than 1 mole, forexample about 5 moles, of the compounds of the formula (IX) per mole ofthe compounds of the formula (VIII) at a reaction temperature in therange of, for example, 0 to 50° C.

The compounds of the formula (X) used as the starting material inprocess (h) include for the most part known compounds.

As examples, there may be exemplified:

6-chloronicotinaldehyde,

6-bromonicotinaldehyde,

6-fluoronicotinaldehyde,

5-acetyl-2-chloropyridine,

5,6-dichloronicotinaldehyde,

5-chloro-6-fluoronicotinaldehyde,

2chloro-4-pyridylcarbaldehyde,

3-chloro-2-pyridinecarbaldehyde,

3,5-dichloro-2-pyridinecarbaldehyde,

5-fluoro-2-pyridinecarbaldehyde,

6-bromo-2-pyridinecarbaldehyde,

2-chloronicotinaldehyde,

5-chloronicotinaldehyde,

5-bromonicotinaldehyde,

5-fluoronicotinaloehyde,

5-acetyl-2-fluoropyridine,

4,6-dichloronicotinaldehyde,

4,6-dibromonicotinaldehyde,

2,6-difluoro-4-pyridinecarbaldehyde,

2-fluoro-4-pyridinecarbaldehyde,

2,6-dibromo-4-pyridinecarbaldehyde,

5-bromo-6-fluoronicotinaldehyde,

6-chloro-5-fluoronicotinaldehyde,

2-chloro-5-propionylpyridine,

nicotinaldehyde,

4-pyridinecarbaldehyde,

6-methylnicotinaldehyde,

6-ethylnicotinaldehyde,

6-allylnicotinaldehyde,

6-propargylnicotinaldehyde,

6-methoxynicotinaldehyde,

6-methylthionicotinaldehyde,

6-methylsulfonylnicotinaldehyde,

6-chloro-4-methylnicotinaldehyde,

3-acetylpyridine,

6-nitronicotinaldehyde,

6-cyanonicotinaldehyde,

6-methylsulfinylnicotinaldehyde,

6-phenylnicotinaldehyde,

6-benzylnicotinaldehyde,

6-phenoxynicotinaldehyde,

6-(2-etboxyethyl)nicotinaldehyde,

6-trichloromethylnicotinaldehyde,

6-methoxymethylnicotinaldehyde,

6-difluoromethoxynicotinaldehyde,

6-trifluoromethoxynicotinaldehyde,

6-(2,2,2-trifluoroethoxy)nicotinaldehyde,

6-chlorodifluoromethylthionicotinaldehyde,

6-trifluoromethylthionicotinaldehyde,

6-difluoromethylnicotinaldehyde,

6-trifluoromethylsulfonylnicotinaldehyde,

6-trifluoromethylsulfinylnicotinaldehyde,

6-(2,2-dichlorovinyl)nicotinaldehyde,

4-pyrimidinecarbaldehyde,

2-methyl-4-pyrimidinecarbaldehyde,

2-methyl-6-oxo-1H,6H-dihydropyrimidine-4-carbaldehyde,

5-pyrimidinecarbaldehyde,

2-methyl-5-pyrimidinecarbaldehyde,

2-dimethylamino-5-pyrimidinecrbaldehyde,

2,4,6-trichloro-5-pyrimidinecarbaldehyde,

pyrazylcarbaldehyde,

acetylpyrazine,

2-methyl-5-pyrazinecarbaldehyde,

3-pyridinecarbaldehyde,

2-chloro-4-pyrimidinecarbaldehyde,

4-chloro-6-pyrimidinecarbaldehyde,

4-methyl-6-pyrimidinecarbaldehyde,

2-fluoro-5-pyrimidinecarbaldehyde,

5-acetyl-2-fluoropyrimidine,

2-chloro-5-pyrimidinecarbaldehyde,

2-isopropyl-5-pyrimidinecarbaldehyde,

2-chlorodifluoromethyl-5-pyrimidinecarbaldehyde,

2-trifluoromethyl-5-pyrimidinecarbaldehyde,

2-bromodifluoromethyl-5-pyrimidinecarbaldehyde,

2-methoxy-5-pyrimidinecarbaldehyde,

2-difluoromethoxy-5-pyrimidinecarbaldehyde,

2-trifluoromethoxy-5-pyrimidinecarbaldehyde,

2-(2,2,2-trifluoroethoxy)-5-pyrimidinecarbaldehyde,

2-methylthio-5-pyrimidinecarbaldehyde,

2-ethylthio-5-pyrimidinecarbaldehyde,

2-difluoroethylthio-5-pyrimidinecarbaldehyde,

2-trifluoromethylthio-5-pyrimidinecarbaldehyde,

2-nitro-5-pyrazinecarbaldehyde,

2-cyano-5-pyrazinecarbaldehyde,

2-chloro-5-pyrazinecarbaldehyde,

2-trifluoromethyl-5-pyrazinecarbaldehyde,

3-fluoro-6-pyridazinecarbaldehyde,

3-methyl-6-pyridazinecarbaldehyde,

4-pyridazinecarbaldehyde,

3-chloro-6-pyridazinecarbaldehyde,

3-trifluoromethyl-6-pyridazinecarbaldehyde,

1,3,5-triazine-2-carbaldehyde,

3-chloro-1,2,4-triazine-6-carbaldehyde,

3,5-dichloro-1,2,4-triazine-6-carbaldehyde, and

3-chloro-1,2,4,5-tetrazine-6-carbaldehyde.

The compounds of the formula (X) can be produced according to variousconventional methods. They will be specifically described below.

For example, the pyridinecarbaldehydes of the formula (X) can beproduced by reacting the corresponding vinylpyridines according toozonolysis reaction (see J. org. chem., vol.26, 4912-4914) and inaccordance with British Patent No. 2,002,368, 6-chloronicotinaldehydecan be derived from 2-chloro-5-pyridylcarbonitrile.

In general, moreover, the formula (X) may be produced withoutdifficulty, according to a conventional method reducing thecorresponding carboxylic acids and the esters thereof or by theVilsmeyer reaction.

For example, pyridinecarbaldehydes also may be produced by reduction ofthe corresponding pyridinecarboxylic acids and the esters thereof (seeOrg. React., vol.8, 218-257).

The formula (X) also may be directly prepared by ring formation. Forexample, with regards to 4-pyrimidinecarbaldehyde, the corresponding2-methylthio-4-methyl-6-pyrimidinecarbaldehyde acetal is obtained byreacting diethoxyacetylacetone with S-methylisothiourea. Subsequestreduction and treatment with hydrochloric acid give4-methyl-6-pyrimidinecarbaldehyde. The use of diethoxyacetylacetonederivatives in this reaction can lead to the synthesis of similarcompounds such as 4-pyrimidinecarbaldehyde,2-methyl-4-pyrimidinecarbaldehyde and2-trifluoromethyl-4-pyrimidinecarbaldehyde (described in Chem. Ber.,vol. 97, pages 3407-3417). Many known methods of synthesizing5-pyrimidinecarbaldehydes are known in the field of organic chemistry.

For example, 5-pyrimidinecarbaldehyde can be synthesized by introducinga formyl group into the 5-position of 4-hydroxy-6-oxodihydropyrimidineby the Vilsmeyer reaction, halogenating the product to form4,6-dichloro-5-formylpyrimidine, and then dehalogenating the resultingcompound (Liebigs Ann. Chem., vol. 766, pages 73-83; and Monatsh. Chem.,vol. 96, pages 1567-1572). By applying this reaction,2-alkyl-substituted and 2-haloalkyl-substituted5-pyrimidinecarbaldehydes can be synthesized. 5-pyrimidinecarbaldehydeshaving other substituents at the 2-position are described in JapaneseLaid-Open Patent Publication No. 59669/1984.

For example, 5-pyrimidinecarbaldehydes having substituents such asalkyl, alkoxy, alkylthio or alkylamino at the 2-position are obtained byreacting{2-[(dimethylamino)-methylene]propanediylidene}bis[dimethylaminoperchlorate](described in Collect. Czech. Chem. Comm., vol. 30, page 2125) withsuitable amidine hydrochlorides.

As regards 5-pyrimidinecarbaldehydes having halogen at the 2-position,2-chloro-5-pyrimidinecarbaldehyde can be obtained, for example, bychlorinating ethyl 2-oxo-1,2-dihydro-5-pyrimidinecarboxylate withphosphorus oxychloride to obtain ethyl 2-chloro-5-pyrimidinecarboxylate(Chem. Pharm. Bull., vol. 12, pages 804-808; a similar example in J.Org. Chem., vol. 29, pages 1740-1743), and reducing the resultingcompound in a customary manner. Since the chlorine atom at the2-position has activity, it may be converted to another substituent suchas 2-fluoro by using potassium fluoride.

With regard to pyridazinecarbaldehydes, 3- and 4-pyridazinecarbaldehydesare described at page 213 of Monatsh. Chem., vol. 108, andmethyl-substituted pyridazinecarbaldehydes, in J. Heterocycle. Chem.,Vol. 17, page 1501.

Moreover, with regard to 5-membered heterocyclic-carbaldehydes, theywill be specifically described below. Furfural is a known compound, andcan easily permit introduction of a halogen atom into the furan ring.For example, 5-chlorofurfural and 4,5-dichlorofurfural can besynthesized from furfural (Zh. Org. Khim., Vol. 11, pages 1955-1958).5-Nitrofurfural is also an easily available known compound.5-Cyano-furfural is a compound described in Tetrahedron, Vol. 39, page3881, and 5-phenoxyfurfural is a compound described in Chem. Pharm.Bull., Vol. 28, No. 9, page 2846. Furancarbaldehydes other thanfurfural, alkyl-substituted, particularly methyl-substituted, furfuralsand other furancarbaldehydes are also known compounds and can be easilyobtained.

Thiophene carbonyl aldehyde is a known compound, and a halogen atom canbe easily introduced into the thiophene ring. For example,2,3-dichloro-4-thiophene carbaldehyde can be synthesized from3-thiophene carbaldehyde (Tetrahedron Vol., 32, pages 1403-1406).2,3-Dibromo-5-thiophene carbaldehyde can be synthesized from2-thiocarbaldehyde (J. Org. Chem., Vol. 41, page 2835).Alkyl-substituted, particularly methyl-substituted, thiophenecarbaldehydes are also known compounds. Alkylthio-substituted orhalogenoalkylthio-substituted thiophenonecarbaldehydes can be obtainedby alkylating or haloalkylating mercapto-substituted thiophenecarbaldehyde. For example, 2-methylthio-5-thiophenecarbaldehyde is aknown compound described in Zh. Obshch. Khim., Vol. 34; pages 4010-4015.Generally, alkylthio-substituted or halogenoalkylthio-substitutedheterocyclic carbaldehydes can be synthesized by the above methods.

Nitro-substituted thiophenonecarbaldehydes can easily be synthesized bynitration of the thiophene ring. For example,4-nitro-2-thiophenecarbaldehyde and 2-nitro-4-thiophenecarbaldehyde areknown compounds described in Bull. Soc. Chim. France, 1963, pages479-484.

Pyrrole carbaldehydes are known compounds. 1-Methyl-2-pyrrolecarbaldehyde can be synthesized from 1-methylpyrrole by the Vilsmeirreaction or by methylating 2-pyrrole carbaldehyde (Beilstein, Vol. 21,I, page 279).

4-iso-Thiazole carbaldehyde can be synthesized from4-isothiazolylcarboxylic acid (J. Medicin. Chem., Vol. 13, pages1208-1212), and 5-isothiazole carbaldehyde can be synthesized from5-isothiazolyl lithium (J. Chem. Soc. 1964, pages 446-451).

5-Pyrazole carbaldehyde and 3-methyl-5-pyrazole carbaldehyde can besynthesized by direct ring synthesis (Chem. Ber., Vol. 97, pages3407-3417). By a similar method, 3-trifluoromethyl-5-pyrazolecarbaldehyde can be synthesized.

A formyl group can be introduced into the 4-position of an N-alkyl orN-aryl pyrazole by the Vilsmeyer reaction. 4-Pyrazole carbaldehyde canbe obtained by eliminating benzyl from N-benzyl-4-pyrazole carbaldehyde(J. Chem. Soc., 1957, pages 3314 and 1115).

4-Methyl-5-imidazole carbaldehyde and 1-methyl-5-imidazole carbaldehydeare known compounds (J. Pharm. Soc. Japan, Vol. 60, pages 184-188; J. A.C. S., Vol. 71, pages 2444-2448).

Many substituted thiazole carbaldehydes are known (Japanese Laid-OpenPatent Publication No. 206,370/1984; Chem. Ab., Vol. 62, 7764d; Chem.Ber., Vol. 101, page 3872). For example, 2-chlorothiazole-5-carbaldehydecan be synthesized by lithiation with butyllithium followed byformulation. Substituted 1,3,4-thiadiazole carbaldehydes are also knowncompounds (Japanese Laid-Open Patent Publication No. 206370/1984).1,2,3-Thiadiazole-5-carbaldehyde is also a known compound (BritishPatent No. 1,113,705).

The compounds of the formula (XI), in the process (h) encompass thecompounds of the aforesaid formula (IX).

In addition, as examples, 2-aminoethanethiol and 3-aminopropanethiol areexemplified (see J. Org. Chem., vol.27, 4712-4713) and theaminoalkanethiols, based on them, also may be included.

For example, in the case of X³ being a sulfur atom, the above process(h) can be carried out in the same way as described in J. Org. Chem.,vol.27, 2452-2457 and 4712-4713.

In carrying out the process (c), as first-step, the thiazolidines or thetetrahydrothiazines can be produced, as intermediate products, byreacting the compounds of the formula (X) with the compounds of theformula (XI) in the presence of inert solvent, such as benzene, and, asnext-step, the intermediates can be reduced by a reducing agent such assodium boron hydride, lithium aluminum hydride, aluminum boron hydride,potassium boron hydride, etc., to produce the compounds of the formula(IIb).

In carring out the process (h) practically, the thiazolidines or thetetrahydrothiazines as intermediate products not only can be obtained bydistilling off volatile matter following the reaction of the first-step,under reduced pressure, for instance, 1 mmHg, at 50-80° C., but also canbe subjected to the reduction directly without the isolation.

In the case of X³ being

according to process (h), the desired compound of the formula (IIb) canbe obtained by heating the starting materials under reflux in an inertsolvent (such as benzene), and directly reducing the reaction mixture ina customary manner without separating the intermediate Schiff base orimine, as will be specifically shown in a working example givenhereinbelow.

In carrying out the process (h), more than 1 mole, for example about 5moles, of the compounds of the formula (XI) are used preferably per moleof the compounds of the formula (X), and the reaction is preferablycarried out under atmospheric pressure at a temperature of usually 0 to100° C.

Moreover, as an alternative process for the preparation of the formula(II) in which X¹ is a sulfur atom, there also may be cited a processwhich comprises halogenating the compounds of the formula (II) in whichX¹ is an oxygen atom by a halogenating agent such as thionylchloride,and thereafter reacting the resulting products with potassium hydrogensulfide.

The compounds of the formula (III), in the process (a), include bothknown and novel compounds.

As examples of known compounds, there may be mentioned: (for example,see Chem. Ber., vol.100, 591-604)

1-nitro-2,2-bis(methylthio)ethylene,

1-nitro-2,2-bis(ethylthio)ethylene,

1-nitro-2,2-bis(benzylthio)ethylene, and

2-nitromethylene-1,3-dithiolane.

The above compounds can be produced in a customary manner whichcomprises reacting nitromethane with carbon disulfide in the presence ofbase and alkylating the resulting product.

If other nitroalkanes are used in place of nitromethane in said process,similar compounds corresponding to the formula (III) may be producedeasily.

In addition, if the acyl-substituted nitromethanes are used in place ofnitromethane in said process, the desired formula (III) may be produced.

For example, if benzoylnitromethane is used,1-benzoyl-1-nitro-2,2-bismethylthioethylene, a novel compound, can beproduced, and if acetylnitromethane is used,1-acetyl-1-nitro-2,2-bis(methylthio)ethylene, a novel compound, can beproduced easily.

The compounds of the formula (IV), in the process (b), are known. (seeChem. Abst., vol.44, 1011F, Japanese Laid-Open Patent Application No.137,473/1984)

As examples, there may be mentioned:

2,2-dichloronitroethylene,

1,2,2-trichloronitroethylene,

1-fluoro-2,2-dichloronitroethylene,

1-methyl-2,2-dichloronitroethylene.

The compounds of the formula (V), in the process (c), are known. (see J.Org. Chem., vol.25, 1312, ibid, vol.28, 1281-1283, Chem. Ber., 75B,1323-1330, Japanese Laid-Open Patent Application No. 48,978/1985)

As examples, there may be mentioned:

2,2,2-trichloro-1-nitroethane,

1,2,2,2-tetrachloro-1-nitroethane,

2,2,2-trifluoro-1-nitroethane.

The formula (VI) provides a general definition of the compounds requiredas a starting material in the process (e), based on aforesaid eachdefinition of n, R¹, R², R³, R⁴, R⁵, R⁶, X, R and Z.

In the formula (VI), n, R¹, R², R³, R⁴, R⁵, R⁶, X, R and Z preferablyhave the meanings already given above.

The compounds of the formula (VI) include both known and novel ones. Forexample, 2-imino-3-(4-pyridylmethyl)thiazolidine has been disclosed inJ. Med. Chem. vol.22, 237-247.

Other compounds of the formula (VI) also can be produced in the same wayas disclosed in the above reference.

The compounds of the formula (VI), for example, can be produced byreacting the aforesaid compounds of the formula (II) with cyanogenhalides.

Said reaction can be easily achieved by mixing the reactants withstirring in inert solvents, and the resulting products can be obtainedin the form of a hydrohalide.

As specific examples of the formula (VI) (in the form of a hydrohalide),there may be mentioned:

Hydrobromides or hydrochiorides of

1-(2-chloro-5-pyridylmethyl)-2-iminoimidazolidine,

1-(2-chloro-5-pyrimidylxnethyl)-2-iminotetrahydropyrimidine

1-(2-fluoro-5-pyridylmethyl)-2-iminoimidazolidine,

1-(2-bromo-5-pyridylmethyl)-2-iminoimidazolidine,

1-(2-trifluoromethyl-5-pyridylmethyl)-2-iminoimidazolidine,

1-(2-methyl-5-pyridylmethyl)-2-iminoimidazolidine,

1-(3-pyridylmethyl)-2-iminoimidazolidine,

1-(3-pyridylmethyl)-2-tetrahydropyrimidine,

1-(2-trifluoromethoxy-5-pyridylmethyl)-2-iminoimidazolidine), and

1-(2-methoxy-5-pyridylmethyl)-2-iminoimidazolidine.

The formula (VII) provides a general definition of the compoundsrequired as a starting material in the process (f), based on aforesaideach definition of n, R¹, R², R³, R⁴, R⁵, R⁶, X and Y.

In the formula (VII), n, R¹, R², R³, R⁴, R⁵, R⁶, X and Y preferably havethe meanings already given above.

The compounds of the formula (VII) are for the most part, known.

As examples, there may be mentioned:

2-nitromethyleneimidazolidine,

2-nitromethylenetetrahydropyrimidine,

4,4-dimethyl-2-nitromethyleneimidazolidine,

3-methyl-2-nitromethyleneimidazolidine,

3-allyl-2-nitromethyleneimidazolidine,

3-propargyl-2-nitromethyleneimidazolidine,

3-(3-chloroallyl)-2-nitromethyleneimidazolidine,

3-acetyl-2-nitromethyleneimidazolidine,

3-chloroacetyl-2-nitromethyleneimidazolidine,

3-benzoyl-2-nitromethyleneimidazolidine,

3-p-tosyl-2-nitromethyleneimidazolidine,

2-nitromethylenethiazolidine,

2-nitromethylene-tetrahydro-2H-1,3-thiazine,

2-nitromethylene-5-methylthiazolidine,

2-nitromethyleneoxazolidine,

2-nitromethylene-4-methyloxazolidine,

2-nitroinethylene-tetrahydro-2H-1,3-oxazine,

2-nitromethylenepyrolidine,

2-nitromethylenepiperidine,

2-(1-nitroethylidene)imidazolidine,

2-(1-nitro-2-fluoroethylidene)imidazolidine,

2-(phenyl, nitromethylene)imidazolidine,

2-(1-nitro-2,2,2-trifluoroethylidene)imidazolidine,

ethyl nitro(imidazolidin-2-ylidene)acetate,

n-butyl nitro(tetrahydropyrimidin-2-ylidene)acetate,

o-tolyl nitro(imidazolidin-2-ylidene)acetate,

p-chlorophenyl nitro(imidazolidin-2-ylidene)acetate,

p-nitrophenyl nitro(imidazolidin-2-ylidene)acetate,

2-(methylthionitromethylene)imidazolidine,

2-(propylthionitromethylene)imidazolidine,

2-[(4-chlorophenylthio)nitromethylene]imidazolidine,

2-(acetylnitromethylene)imidazolidine,

2-(dinitromethylene)imidazolidine,

2-(benzoylnitromethylene)imidazolidine,

ethyl nitro(1-ethoxycarbonylimidazolidin-2-ylidene)acetate,

phenyl nitro(1-phenylthiocarbonylimidazolidin-2-ylidene)thiolacetate,

2-(phenylthionitromethylene)-1-phenylthioimidazolidine,

2-(1-nitroethylidene)-tetrahydro-2H-1,3-thiazine,

2-(1-nitro-3-butynylidene)thiazolidine.

2-(1-nitro-3-butynylidene)-tetrahydro-2H-1,3-thazine,

2-(1-nitro-2-phenylethylidene)thiazolidine,

2-(3-acetyl-1-nitropropylidene)-tetrahydro-2H-1,3-thiazine,

2-(3-cyano-1-nitropropylidene)-tetrahydro-2H-1,3-thazine,

methyl 4-nitro-4-(thiazolidin-2-ylidene)butyrate,

2-(2-ethylthio-1-nitroethylidene)-tetrahydro-2H-1,3-thiazine,

2-(2-dimethylamino-1-nitroethylidene)thiazolidine,

ethyl nitro(tetrahydro-2H-1,3-thazin-2-ylidene)acetate,

phenyl nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetate,

2-formylnitromethylenethiazolidine,

2-acetylnitromethylene-tetrahydro-2H-1,3-thiazine,

2-benzoylnitromethylene-tetrahydro,-2H-1,3-thiazine,

2-phenylthionitromethylene-tetrahydro-2H-1,3-thiazine,

ethyl nitro(oxazolidin-2-ylidene)acetate,

ethyl nitro(tetrahydro-2H-1,3-oxazin-2-ylidene)acetate,

3-methyl-2-nitromethylenepyrolidine,

3-fluoro-2-nitromethylenepiperidine,

methyl nitro(pyrrolidin-2-ylidene)acetate,

3-methylthio-2-nitromethylenepiperidine,

ethyl nitro(thiazolidine-2-ylidene)acetate,

2-nitroiminoimidazolidine,

4,4-dimethyl-2-nitroiminoimidazolidine,

2-nitroiminotetrahydropyrimidine,

3-methyl-2-nitroiminoimidazolidine,

3-isopropyl-2-nitroiminoimidazolidine,

3-(2-ethoxyethyl)-2-nitroiminoimidazolidine,

3-ethoxycarbonyl-2-nitroiminoimidazolidine,

3-phenylthio-2-nitroiminoimidazolidine,

3-formyl-2-nitroiminoimidazolidine,

3-acetyl-2-nitroiminotetrahydropyrimidine,

3-(2-bromo-3,3-dimethylbutylyl)-2-nitroimidazolidine,

3-(2-trifluoromethylbenzoyl)-2-nitroiminoimidazolidine,

3-(2,4-dichloro-3-methylbenzoyl)-2-nitroiminoimidazolidine,

3-(4-methoxybenzoyl)-2-nitroiminoimidazolildine,

3-(3-chloropropylsulfonyl)-2-nitroiminoimidazolildine,

3-(2-difluoromethoxybenzoyl)-2-nitroiminotetrahydropyrimidine,

3-phenoxycarbonyl-2-nitroiminoimidazolidine,

3-(2-froyl)-2-nitroiminotetrahydropyrimidine,

3-(2-methylthiazole-5-ylcarbonyl)-2-nitroiminoimidazolidine,

3-(diethoxyphosphono)-2-nitroiminoimidazolidine,

3-(5-nitro-2-methylbenzenesulfonyl)-2-nitroiminoimidazolidine,

2-nitroiminothiazolidine,

2-nitroiminotetrahydro-2H-1,3-thiazine,

2-nitroiminoxazolidine,

4 -methyl-2-nitroiminoxazolidine,

2-nitroiminopyrrolidine,

2-nitroiminopiperidine,

3-methyl-2-nitroiminopyrrolidine, and

2-nitroiminotetrahydro-2H-1,3-oxazine.

2-nitromethylene-imidazolidines (or tetrahydropyrimidines), of the abovesaid formula (VII), are known compounds (see, for instance, Chem. Ber.,vol.100, 591-604, Belgian Patent No. 821, 281, U.S. Pat. No. 3,971,774).

In addition, N-acyl derivatives from 2-nitromethylene-imidazolidines (ortetrahydropyrimidines) can be produced by known processes (see JapaneseLaid-Open Patent Application Nos. 67,473/1985 and 61,575/1985).

Moreover, in the case of another group, besides a nitro group, beingattached to the methylene group of 2-nitromethylene-imidazolidines (ortetrahydropyrimidines), said compounds of the formula (VII) can beproduced, in accordance with the known process described in U.S. Pat.Nos. 3,996,372, 4,002,765, 4,042,696, 4,052,411, 4,053,619, 4,053,622and 4,053,623 and Japanese Laid-Open Patent Application No. 151,727/1977and Belgian Patent No. 821,282.

2-nitromethylene-thiazolidines (or tetrahydro-2H-1,3-thiazines) arealso, for the most part, known compounds which can be easily produced,for instance, by reacting aminoalkanethiols with the aforesaid formula(III) that may be replaced by the aforesaid formula (IV) or formula (V).

Moreover, 2-position of 2-nitromethylene-thiazolidines (ortetrahydro-2H-1,3-thiazines) may be substituted by various knownprocesses to obtain desired starting materials of the formula (VII).(see U.S. Pat. Nos. 3,962,234, 4,022,775, 4,024,254, 4,044,128,4,045,434 and 4,076,813, and Japanese Laid-Open Patent Application No.151,882/1975)

2-nitromethylene-oxazolidines (or -tetrahydro-2H-1,3-oxazines) are alsoknown compounds which can be produced by reacting aminoalkanols with theaforesaid formula (III) that may be replaced by the aforesaid formula(IV) or formula (V). [see Adv. Pestic. Sci., Plenary Lect. Symp. Pap.Int. Congr. Pestic. Chem. 4-th, 1978, 206-217 (ref. Chem. abst., vol.91,103,654), U.S. Pat. No. 3,907,790, Japanese. Laid-Open PatentApplication Nos. 151,882/1975 and 151,727/1977]

2-nitromethylene-pyrrolidines (or piperidines) are also known compoundswhich, for example, can be produced by reacting 2-methoxypyrroline-1with nitroalkanes. (see Netherland Patent Nos. 7,306,020 and 7,306,145)

2-nitroimino derivatives of the formula (VII) are also known compounds.

For instance, 2-nitroiminooxazolidines are described in J. Am. Chem.Soc., vol.73, 2213-2216.

2-nitroiminoimidazolidines, 2-nitroiminotetrahydropyrimidines andN-acetyl derivatives thereof are described in J. Am. Chem. Soc., vol.73,2201-2205 and British Patent No. 2,055,796.

N-acyl derivatives, excluding N-acetyl derivatives, N-sulfenylderivatives, N-sulfonyl derivatives and N-phosphono derivatives arenovel compounds which may be produced in the same way as described inBritish Patent No. 2,055,796.

2-nitroimino-thiazolidines (or tetrahydro-2H-1,3-thiazines,2-nitroimino-pyrrolidines or (piperidines) which can be produced byreacting nitroguanidine with the diamines, the aminoalkanols or theaminoalkanethiol, or by reacting 2-imino compound with nitric acid inthe presence of sulfuric acid are also described in the aforesaidBritish Patent.

The formula (VIII) provides a general definition of the compoundsrequired as a starting material in the process (f), based on aforesaideach definition of Z and R.

In the formula (VIII), Z and R preferably have the meanings alreadygiven above.

The compounds of the formula (VIII) usable according to the inventioninclude known compounds, for instance, those already disclosed in J.Org. Chem. , vol.34, 3547, J. Medicin. Chem., vol.14, 211-213 and557-558, 1971, U.S. Pat. No. 4,332,944, J. Heterocycl. Chem., 1979,vol.16, 333-337.

As examples, there may be mentioned:

3-picolyl chloride,

1-(3-pyridyl)ethyl chloride,

1-(3-pyridyl)propyl chloride,

2-methyl-1-(3-pyridyl)propyl chloride,

4-picolyl chloride,

5-chloro-2-pyridylmethyl chloride,

2-fluoro-5-pyridylmethyl chloride,

2-chloro-5-pyridylmethyl chloride,

1-(2-chloro-5-pyridyl)ethyl chloride,

2-nitro-5-pyridylmethyl chloride,

2-cyano-5-pyridylmethyl chloride,

2-amino-5-pyridylmethyl chloride,

2-acetamide-5-pyridylmethyl chloride,

2-dimethylamino-5-pyridylmethyl chloride,

2-ethoxycarbonyl-5-pyridylmethyl chloride,

2-acetyl-5-pyridylmethyl chloride,

2-chloro-3-methyl-5-pyridylmethyl chloride,

2-difluoromethyl-5-pyridylmethyl chloride,

5-trifluoromethyl-2-pyridylmethyl chloride,

2-bromodifluoromethyl-5-pyridylmethyl chloride,

2-chlorodifluoromethyl-5-pyridylmethyl chloride,

2-trichloromethyl-5-pyridylmethyl chloride,

2-(2-chloroethyl)-5-pyridylmethyl chloride,

2-(2-fluoroethyl)-5-pyridylmethyl chloride,

2-(2,2,2-trifluoroethoyl)-5-pyridylmethyl chloride,

2-difluoroethoxy-5-pyridylmethyl chloride,

2-trifluoromethoxy)-5-pyridylmethyl chloride,

2-(2,2,2-trifluoroethoxy)-5-pyridylmethyl chloride,

2-(trifluoromethylthio)-5-pryridylmethyl chloride,

2-formyl-5-pyridylmethyl chloride,

2-chlorodifluoromethylthio-5-pyridylmethyl chloride,

2-(2,2-dichlorovinyl)-5-pyridylmethyl chloride,

5-trifluoromethyl-2-pyridylmethyl chloride,

5-methyl-2-pyridylmethyl chloride,

6-methyl-2-pyridylmethyl chloride,

4-methyl-2-pyridylmethyl chloride,

5-ethyl-2-pyridylmethyl chloride,

5-butyl-2-pyridylmethyl chloride,

4,6-dimethyl-2-pyridylmethyl chloride,

3-chloro-2-pyridylmethyl chloride,

3,5-dichloro-2-pyridylmethyl chloride,

5-fluoro-2-pyridylmethyl chloride,

6-bromo-2-pyridylmethyl chloride,

6-chloro-4-methyl-2-pyridylmethyl chloride,

5-methyl-3-pyridylmethyl chloride,

2-methyl-5-pyridylmethyl chloride,

2-chloro-3-pyridylmethyl chloride,

5-chloro-3-pyridylmethyl chloride,

5-bromo-3-pyridylmethyl chloride,

2-bromo-5-pyridylmethyl chloride,

5-fluoro-3-pyridylmethyl chloride,

2-fluoro-5-pyridylmethyl chloride,

1-(2-fluoro-5-pyridyl)ethyl chloride,

2-methyl-1-(2-fluoro-5-pyridyl)propyl chloride,

2-chloro-6-methyl-3-pyridylmethyl chloride,

2,4-dichloro-5-pyridylmethyl chloride,

2,6-dichloro-5-pyridylmethyl chloride,

2,4-dibromo-5-pyridylmethyl chloride,

2,4-difluoro-5-pyridylmethyl chloride,

2-methoxy-3-pyridylmethyl chloride,

2-methoxy-5-pyridylmethyl chloride,

2-ethoxy-5-pyridylmethyl chloride,

2-isopropoxy-5-pyridylmethyl chloride,

2-methylthio-3-pyridylmethyl chloride,

2-methylthio-5-pyridylmethyl chloride,

4-methyl-2-methylthio-5-pyridylmethyl chloride,

2-ethylthio-5-pyridylmethyl chloride,

2-methylsulfinyl-5-pyridylmethyl chloride,

2-methylsulfonyl-5-pyridylmethyl chloride,

4-chloro-2-fluoro-5-pyridylmethyl chloride,

6-chloro-2-methyl-3-pyridylmethyl chloride,

2-chloro-4-methyl-5-pyridylmethyl chloride,

2-allyl-5-pyridylmethyl chloride,

2-propargyl-5-pyridylmethyl chloride,

2,3-dichloro-5-pyridylmethyl chloride,

2-(1-propenyl)-5-pyridylmethyl chloride,

2-chloro-4-pyridylmethyl chloride,

2-fluoro-4-pyridylmethyl chloride,

2,6-dichloro-4-pyridylmethyl chloride,

2,6-difluoro-4-pyridylmethyl chloride,

2-methyl-4-pyridylmethyl chloride,

1-(2-chloro-4-pyridyl)ethyl chloride,

2-chloro-6-methyl-4-pyridylmethyl chloride,

2,6-dimethyl-4-pyridylmethyl chloride,

2-bromo-4-pyridylmethyl chloride,

2,6-dibromo-4-pyridylmethyl chloride,

3-chloro-2-fluoro-5-pyridylmethyl chloride,

3-bromo-2-fluoro-5-pyridylmethyl chloride,

2-chloro-3-fluoro-5-pyridylmethyl chloride,

3-chloro-2-methylthio-5-pyridylmethyl chloride,

2-ethyl-5-pyridylmethyl chloride,

2-phenyl-5-pyridylmethyl chloride,

2-benzyl-5-pyridylmethyl chloride,

2-phenoxy-5-pyridylmethyl chloride,

2-(2-ethoxyethyl)-5-pyridylmethyl chloride,

2-methoxymethyl-5-pyridylmethyl chloride,

2-difluoromethoxy-5-pyridylmethyl chloride,

2-(2,2,2-trifluoroethoxy)-5-pyridylmethyl chloride,

2-trifluoromethylsulfonyl-5-pyridylmethyl chloride,

2-trifluoromethylsulfinyl-5-pyridylmethyl chloride,

3-furylmethyl chloride,

furfuryl chloride,

5-methylfurfuryl chloride,

2-thienylmethyl chloride,

4-imidazolylmethyl chloride,

4-methyl-5-imidazolylmethyl chloride,

tetrahydrofurfuryl chloride,

5-methyltetrahydrofurfuryl chloride,

3-thienylmethyl chloride,

2-pyrrolylmethyl chloride,

1-methyl-2-pyrrolylmethyl chloride,

5-methyl-2-thienylmethyl chloride,

5-bromo-2-thienylmethyl chloride,

5-cyanofurfuryl chloride,

5-trifluoromethylthio-2-thienylmethyl chloride,

1-(2-thienyl)ethyl chloride,

5-methyl-3-isoxazolylmethyl chloride,

5-isoxazolylmethyl chloride,

4-isoxazolylmethyl chloride,

3-methyl-5-isoxazolylmethyl chloride,

3-trifluoromethyl-5-isoxazolylmethyl chloride,

3-chloro-5-isoxazolylmethyl chloride,

5-isothiazolylmethyl chloride,

5-pyrazolylmethyl chloride,

4-pyrazolylmethyl chloride,

1-methyl-4-pyrazolylmethyl chloride,

1-(1-methyl-4-pyrazolyl)ethyl chloride,

1-ethyl-4-pyrazolylmethyl chloride,

1-isopropyl-4-pyrazolylmethyl chloride,

1-allyl-4-pyrazolylmethyl chloride,

1-tert-butyl-4-pyrazolylmethyl chloride,

1-(2,2,2-trifluoroethyl)-5-pyrazolylmethyl chloride,

3-methyl-5-pyrazolylmethyl chloride,

3-chloro-2-methyl-5-pyrazolylmethyl chloride,

2,3,5-trimethyl-4-pyrazolylmethyl chloride,

5-oxazolylmethyl chloride,

4-methyl-5-oxazolylmethyl chloride,

4-thiazolylmethyl chloride,

5-thiazolylmethyl chloride,

2-methyl-5-thiazolylmethyl chloride,

2-chloro-4-thiazolylmethyl chloride,

2-chloro-5-thiazolylmethyl chloride,

2-trifluoromethyl-5-thiazolylmethyl chloride,

2-bromo-5-thiazolylmethyl chloride,

2,4-dichloro-5-thiazolylmethyl chloride,

4-imidazolylmethyl chloride,

1-methyl-2-imidazolylmethyl chloride,

1,2,4-triazol-5-ylmethyl chloride,

1-methyl-1,2,4-triazol-3-ylmethyl chloride,

1,2,5-thiadiazol-4-ylmethyl chloride,

1,2,3-thiadiazol-5-ylmethyl chloride,

3-methyl-1,2,4-oxadiazol-5-ylmethyl chloride,

1,3-dioxolan-2-ylmethyl chloride,

2,2-dimethyl-1,3-dioxolan-4-ylmethyl chloride,

2-methyl-2-oxazolin-5-ylmethyl chloride,

2-trifluoromethyl-2-oxazolin-5-ylmethyl chloride,

3-pyrrolylmethyl chloride,

1-ethyl-2-pyrrolylmethyl chloride,

1-methyl-3-pyrrolylmethyl chloride,

5-methyl-3-thienyl chloride,

5-methyl-3-pyrrolylmethyl chloride,

1,5-dimethyl-3-pyrrolylmethyl chloride,

2,5-dimethyl-3-furylmethyl chloride,

2,5-dimethyl-3-thienylmethyl chloride,

5-fluoro-3-furylmethyl chloride,

4-chlorofurfuryl chloride,

5-chlorofurfuryl chloride,

5-chloro-3-furylmethyl chloride,

5-chloro-3-thienylmethyl chloride,

5-chloro-1-methyl-3-pyrrolylmethyl chloride,

5-bromo-3-furylmethyl chloride,

5-nitrofurfuryl chloride,

4-nitro-2-thienylmethyl chloride,

5-nitro-2-thienylmethyl chloride,

1-methyl-5-nitro-3-pyrrolylmethyl chloride,

5-cyano-3-furylmethyl chloride,

5-cyano-3-thienylmethyl chloride,

5-cyano-1-methyl-3-pyrrolylmethyl chloride,

5-trifluoromethylfurfuryl chloride,

5-difluoromethylfurfuryl chloride,

5-trifluoromethyl-3-thienylmethyl chloride,

1-methyl-5-trifluoromethyl-3-pyrrolylmethyl chloride,

5-methoxy-2-thienylmethyl chloride,

5-methylfurfuryl chloride,

2,5-dimethylthio-3-thienylmethyl chloride,

5-trifluoromethylthiofurfuryl chloride,

5-(2,2-dichlorovinyl)-2-thienylmethyl chloride,

5-ethoxycarbonylfurfuryl chloride,

5-formyl-2-thienylmethyl chloride,

3-isoxazolylmethyl chloride,

4-isoxazolylmethyl chloride,

3-ethyl-5-isoxazolylmethyl chloride,

3-isopropyl-5-isoxazolylmethyl chloride,

3-fluoro-5-isoxazolylmethyl chloride,

3-bromo-5-isoxazolylmethyl chloride,

3-hydroxy-5-isoxazolylmethyl chloride,

3-nitro-5-isoxazolylmethyl chloride,

3-cyano-5-isoxazolylmethyl chloride,

3-difluoromethyl-5-isoxazolylmethyl chloride,

3-chlorodifluoromethyl-5-isoxazolylmethyl chloride,

3-methoxymethyl-5-isoxazolylmethyl chloride,

3-isopropoxymethyl-5-isoxazolylmethyl chloride,

3-trichloromethyl-5-isoxazolylmethyl chloride,

3-methoxy-5-isoxazolylmethyl chloride,

3-trifluoromethoxy-5-isoxazolylmethyl chloride,

2,5-dimethyl-4-isoxazolylmethyl chloride,

3-isothiazolylmethyl chloride,

4-isothiazolylmethyl chloride,

3-pyrazolylmethyl chloride,

1-(4-pyrazolyl)ethyl chloride,

1-methyl-3-pyrazolylmethyl chloride,

1-methyl-5-pyrazolylmethyl chloride,

1-propyl-4-pyrazolylmethyl chloride,

1-(2,2,2-trifluoroethyl)-3-pyrazolylmethyl chloride,

5-chloro-1-ethyl-3-pyrazolylmethyl chloride,

5-chloro-1-isopropyl-3-pyrazolylmethyl chloride,

3-chloro-1-methyl-5-pyrazolylmethyl chloride,

5-trifluoromethyl-3-pyrazolylmethyl chloride,

1-methyl-5-trifluoromethyl-3-pyrazolylmethyl chloride,

1-methyl-3-trifluoromethyl-5-pyrazolylmethyl chloride,

4-oxazolylmethyl chloride,

2-methyl-4-oxazolylmethyl chloride,

2-methyl-5-oxazolylmethyl chloride,

2-fluoro-5-oxazolylmethyl chloride,

2-chloro-5-oxazolylmethyl chloride,

2-trifluoromethyl-5-oxazolylmethyl chloride,

2-methylthio-5-oxazolylmethyl chloride,

2-trifluoromethoxy-5-oxazolylmethyl chloride,

2,4-dimethyl-5-oxazolylmethyl chloride,

5-ethoxycarbonyl-2-oxazolylmethyl chloride,

1-(5-thiazolyl)ethyl chloride,

2-methyl-4-thiazolylmethyl chloride,

1-(2-methyl-5-thiazolyl)ethyl chloride,

2-ethyl-5-thiazolylmethyl chloride,

2-isopropyl-5-thiazolylmethyl chloride,

4-methyl-5-thiazolylmethyl chloride,

2-fluoro-4-thiazolylmethyl chloride,

2-fluoro-5-thiazolylmethyl chloride,

1-(2-chloro-5-thiazolyl)ethyl chloride,

2-nitro-4-thiazolylmethyl chloride,

2-nitro-5-thiazolylmethyl chloride,

2-cyano-4-thiazolylmethyl chloride,

2-cyano-5-thiazolylmethyl chloride,

2-methylthio-4-thiazolylmethyl chloride,

2-mercapto-5-thiazolylmethyl chloride,

2-methylthio-5-thiazolylmethyl chloride,

2-difluoromethylthio-5-thiazolylmethyl chloride,

2-trifluoromethylthio-5-thiazolylmethyl chloride,

2-chlorodifluoromethylthio-5-thiazolylmethyl chloride,

2-(2,2,2-trifluoroethylthio)-5-thiazolylmethyl chloride,

2-[2-(2,3,3-trichloro)propenylthio]-thiazolylmethyl chloride,

2-thiocyanato-5-thiazolylmethyl chloride,

2-amino-4-thiazolylmethyl chloride,

2-acetamino-4-thiazolylmethyl chloride,

2-methoxy-4-thiazolylnethyl chloride,

2-methoxy-5-thiazolylmethyl chloride,

2-trifluoromethoxy-5-thiazolylmethyl chloride,

2-difluoromethoxy-5-thiazolylmethyl chloride;

2-chloromethyl-5-thiazolylmethyl chloride,

2-difluoromethyl-5-thiazolylmethyl chloride,

2-trifluoromethyl-5-thiazolylmethyl chloride,

2-(1,1,2,2-tetrafluoroethyl)-5-thiazolylmethyl chloride,

2-cyclopropyl-5-thiazolylmethyl chloride,

2-imidazolylmethyl chloride,

1-methyl-5-imidazolylmethyl chloride,

2-fluoro-4-imidazolylmethyl chloride,

2-chloro-4-imidazolylmethyl chloride,

4-nitro-2-imidazolylmethyl chloride,

2-trifluoromethylthio-4-imidazolylmethyl chloride,

1,2-dimethyl-4-imidazolylmethyl chloride,

1-methyl-2-trifluoromethyl-4-imidazolylmethyl chloride,

1-methyl-1,2,3-triazol-4-ylmethyl chloride,

1-(1-methyl-1,2,3-triazol-4-yl)ethyl chloride,

3-methyl-1,2,4-triazol-5-ylmethyl chloride,

3-trifluoromethyl-1,2,4-triazol-5-ylmethyl chloride,

1,2,4-oxadiazol-5-ylmethyl chloride,

1,3,4-oxadiazol-2-ylmethyl chloride,

1,2,3-oxadiazol-5-ylmethyl chloride,

3-trifluoromethyl-1,2,4-oxadiazol-5-ylmethyl chloride,

2-methyl-1,3,4-oxadiazol-5-ylmethyl chloride,

2-trifluoromethyl-1,3,4-oxadiazol-5-ylmethyl chloride,

2-(2,2,2-trifluoroethyl)-1,3,4-oxadiazol-5-ylmethyl chloride,

1,2,4-thiadiazol-5-ylmethyl chloride,

1,2,3-thiadiazol-4-ylmethyl chloride,

1-(1,2,3-thiadiazol-5-yl)ethyl chloride,

1,3,4-thiadiazol-2-ylmethyl chloride,

1-(1,3,4-thiadiazol-2-yl)ethyl chloride,

1,2,5-thiadiazol-3-ylmethyl chloride,

3-methyl-1,2,4-thiadiazol-5-ylmethyl chloride,

4-methyl-1,2,3-thiadiazol-5-ylmethyl chloride,

2-methyl-1,3,4-thiadiazol-5-ylmethyl chloride,

2-trifluoromethyl-1,3,4-thiadiazol-5-ylmethyl chloride,

2-fluoro-1,3,4-thiadiazol-5-ylmethyl chloride,

2-chloro-1,3,4-thiadiazol-5-ylmethyl chloride,

3-chloro-1,2,5-thiadiazol-4-ylmethyl chloride,

1-(3-tetrahydrofuryl)ethyl chloride,

3-tetrahydrothienylmethyl chloride,

1-(3-tetrahydrothienyl)ethyl chloride,

1-methyl-3-pyrrolydinylmethyl chloride,

1,3-oxathiolan-2-ylmethyl chloride,

1,3-dioxolan-4-ylmethyl chloride,

1,3-oxathiolan-4-ylmethyl chloride,

1,3-dithiolan-4-ylmethyl chloride,

thiazolidin-5-ylmethyl chloride,

4-methyl-3-dioxolan-2-ylmethyl chloride,

2-methyl-1,3-oxathiolan-4-ylmethyl chloride,

2-chloromethyl-1,3-dioxolan-4-ylmethyl chloride,

2-trifluoromethyl-1,3-dioxolan-4-ylmethyl chloride,

2-oxo-1,3-dioxolan-4-ylmethyl chloride,

3-formyl-thiazolidin-5-ylmethyl chloride,

3-acetyl-thiazolidin-5-ylmethyl chloride,

3-thiolen-5-ylmethyl chloride,

2H,5H-1,1-dioxo-3-thiolen-3-ylmethyl chloride,

2-isoxazolin-5-ylmethyl chloride,

3-methyl-2-isoxazolin-5-ylmethyl chloride,

3-trifluoromethyl-2-isoxazolin-5-ylmethyl chloride,

3-(2,2,2-trifluoroethyl)-2-isoxazolin-5-ylmethyl chloride,

2,4-dimethyl-2-oxazolin-4-ylmethyl chloride,

2-methyl-1,3-thiazolin-4-ylmethyl chloride,

2-oxazolidon-5-ylmethyl chloride,

3-methyl-2-thiazolidinon-5-ylmethyl chloride,

2-methylamino-5-thiazolylmethyl chloride,

2-trifluoroacetamide-5-thiazolylmethyl chloride,

3-methyl-2-thioxo-thiazolidin-5-ylmethyl chloride,

3-chloro-1,2,4-oxadiazol-5-ylmethyl chloride,

5-carboxy-2-oxazolylmethyl chloride,

2-dimethylamino-5-thiazolylmethyl chloride,

5-phenoxyfurfuryl chloride,

1-phenyl-4-pyrazolylmethyl chloride,

1-benzyl-4-pyrazolylmethyl chloride,

2-phenyl-4-thiazolylmethyl chloride,

1-benzyl-2-imidazolylmethyl chloride,

2-methylsulfinyl-5-thiazolylmethyl chloride,

2-methylsulfonyl-5-thiazolylmethyl chloride,

2-carbamoyl-5-thiazolylmethyl chloride,

2-methylaminocarbonyl-5-thiazolylmethyl chloride,

2-dimethylaminocarbonyl-5-thiazolylmethyl chloride,

5-methylthio-1,3,4-thiadiazol-2-ylmethyl chloride,

5-methylsulfonyl-1,3,4-thiadiazol-2-ylmethyl chloride,

4-pyrimidinylmethyl chloride,

2-methyl-4-pyrimidinylmethyl chloride,

2-methyl-6-oxo-1H,6H-dihydropyrimidin-4-ylmethyl chloride,

5-pyrimidinylmethyl chloride,

2-methyl-5-pyrimidinylmethyl chloride,

2-dimethylamino-5-pyrimidinylmethyl chloride,

2,4,6-trichloro-5-pyrimidinylmethyl chloride,

pyrazinylmethyl chloride,

1-(pyrazinyl)ethyl chloride,

2-methyl-5-pyrazinylmethyl chloride,

3-pyridazinylmethyl chloride,

2-chloro-4-pyrimidinylmethyl chloride,

4-chloro-6-pyrimidinylmethyl chloride,

4-methyl-6-pyrimidinylmethyl chloride,

2-fluoro-5-pyrimidinylmethyl chloride,

1-(2-fluoro-5-pyrimidinyl)ethyl chloride,

2-chloro-5-pyrimidinylmethyl chloride,

2-isopropyl-5-pyrimidinylmethyl chloride, or bromide,

2-chlorodifluoromethyl-5-pyrimidinylmethyl chloride,

2-trifluoromethyl-5-pyrimidinylmethyl chloride,

2-bromodifluoromethyl-5-pyrimidinylmethyl chloride,

2-methoxy-5-pyrimidinylmethyl chloride,

2-difluoromethoxy-5-pyrimidinylmethyl chloride,

2-trifluoromethoxy-5-pyrimidinylmethyl chloride,

2-(2,2,2-trifluoroethoxy)-5-pyrimidinylmethyl chloride,

2-methylthio-5-pyrimidinylmethyl chloride,

2-ethylthio-5-pyrimidinylmethyl chloride,

2-difluoroethylthio-5-pyrimidinylmethyl chloride,

2-trifluoromethylthio-5-pyrimidinylmethyl chloride,

2-nitro-5-pyrazinylmethyl chloride,

2-cyano-5-pyrazinylmethyl chloride,

2-chloro-5-pyrazinylmethyl chloride,

2-trifluoromethyl-5-pyrazinylmethyl chloride,

3-fluoro-6-pyridazinylmethyl chloride,

3-methyl-6-pyridazinylmethyl chloride,

4-pyridazinylmethyl chloride,

3-chloro-6-pyridazinyl methyl chloride,

4-pyridazinylmethyl chloride,

3-trifluoromethyl-6-pyridazinylmethyl chloride,

1,3,5-triazin-2-ylmethyl chloride,

3-chloro-1,2,4-triazin-6-ylmethyl chloride,

3,5-dichloro-1,2,4-triazin-6-ylmethyl chloride, and

3-chloro-1,2,4,5-tetrazin-6-ylmethyl chloride.

In place of the chlorides hereinabove, the bromides or thep-toluensulfonates may also be exemplified. They will be specificallydescribed below.

The halides hereinabove, for instance the chlorides, can be producedwithout difficulty by chlorination of the corresponding alcohols withthionylchloride.

For instance, 2-chloro-5-pyridylmethylchloride can be obtained bychlorination of 2-chloro-5-pyridylmethylalcohol with thionylchloride.(see J. Org. Chem., vol. 34, 3547)

The bromides may also be produced by bromination of a methyl groupside-chain with N-bromosuccinimide.

Some of trifluoromethyl-substituted or trifluoromethoxy-substitutedpyridyl alcohols are described in J. Med. Chem., vol. 13, pages1124-1130. By using these synthesizing techniques,2-methyl-5-trifluoromethyl pyridine obtained by reaction of6-methylnicotinic acid with hydrofluoric acid and sulfur tetrafluorideis converted to an N-oxide, and the rearrangement reaction of theN-oxide can give 5-trifluoromethyl-2-pyridylmethyl alcohol.

This reaction can also be applied to the synthesis of5-methyl-2-trifluoromethylpyridine from 5-methylpicolic acid.2-Trifluoromethyl-5-pyridylmethyl bromide (or chloride), the desiredstarting substance, can be synthesized by mono-halogenating theaforesaid 5-methyl-2-trifluoromethylpyridine with N-bromosuccinimide orN-chlorosuccinimide.

2-Trifluoromethoxy-5-pyridylmethyl bromide (or chloride) can similarlybe obtained by reacting 5-methyl-2-trifluoromethoxypyridine obtainedfrom 2-hydroxy-5-methylpyridine, with N-bromosuccinimide orN-chlorosuccinimide.

Since the halogen at the ortho-position of the pyridine ring is active,a 2-haloalkoxy-5-pyridylmethyl alcohol can be synthesized, for example,by the reaction of 6-chloronicotinic acid with an excess of a sodiumalkoxide. Reduction of this compound can give the starting2-haloalkoxy-5-pyridylmethyl alcohol.

Halogenomethyl-substituted furans and thiophenes are known compounds.For example, 2-ethoxycarbonyl-5-chloromethylfuran is a known compounddescribed in Liebigs Annalen der Chemie, Vol. 580, page 176.2-Bromomethyl-5-trifluoromethylfuran is obtained by halogenating theside-chain of 2-methyl-5-trifluoromethylfuran with a halogenating agentsuch as N-bromosuccinimide (NBS) (U.S. Pat. No. 3,442,913).

Many bromomethyl-substituted heterocyclic compounds can be obtained bybrominating the corresponding methyl-substituted heterocyclic compoundswith N-bromosuccinimide.

Halogenomethyl-substituted isoxazoles can be obtained by halogenatingmethylisoxazole with NBS, etc. or hydroxymethyl isoxazole can be easilyconverted to chloromethyl isoxazole by thionyl chloride. For example,5-bromomethyl isoxazole is a compound described in GermanOffenlegungsschrift No. 2,716,687, and 4-bromomethylisoxazole is acompound described in Chem. Abst., Vol. 65, 2242h.

Chloromethyl-substituted heterocyclic compounds can be synthesized bychloromethylation reaction. 4-chloromethyl isoxazole and4-chloromethyl-3,5-dimethylisoxazole described in Zh. Obshch. Khim.,Vol. 34, pages 4010-4015 are good examples thereof. Furthermore,halogenomethyl-substituted isoxazoles can also be synthesized by directring synthesis. 3-Bromo-5-bromomethylisoxazole (Rend. Ist. Lombardo Sci.Pt. I. Classe Sci. Mat. e Nat., Vol. 94, pages 729-740, and5-bromomethyl-3-methylisoxazole (Japanese Laid-Open Patent PublicationNo. 59156/1977) are good examples thereof.

5-Chloromethyl-3-trifluoromethyl isoxazole can be obtained bysynthesizing 3-trifluoromethyl-5-hydroxymethyl isoxazole, andchlorinating it with thionyl chloride in accordance with the descriptionof Bull. Chem. Soc. Japan, Vol. 57, pages 2184-2187. The use of otherhalogenoalkyls instead of trifluoromethyl in the above reaction can leadto the synthesis of the corresponding halogenoalkyl isoxazoles. Asstated above, halogenoalkyl heterocyclic compounds can be easilyobtained generally by treating the corresponding alcohols withhalocenating agents typified by thionyl chloride.

5-Chloromlethyl-3-hydroxyisoxazole is synthesized in accordance with thedescription of Tetrahedron Letters, 1965, No. 25, pages 2077-2079.Chlorination of it with phosphonyl chloride, etc., can give3-chloro-5-chloromethyl isoxazole.

Halogen-substituted halogenomethyl-substituted isothiazoles can beobtained, for example, by converting halogen-substitutedmethyl-substituted isothiazoles with halogenating agents such as NBSinto halogen-substituted bromomethyl-substituted isothiazoles.5-Bromo-3-bromomethylisothiazole (described in J. Chem. Soc., 1965,pages 7274-7276) is a good example.

4-Chloromethylpyrazole can be easily obtained by chlorinating4-hydroxymethylpyrazole with thionyl chloride (J. A. C. S., Vol. 71,pages 3994-4000).

As regards halogeno-halogenomethylpyrazoles,3-ethoxycarbonyl-5-hydroxy-1-methylpyrazole, for example, is synthesizedin accordance with the description of Chem. Pharm. Bull., Vol. 31, No.4, pages 1228-1234. Subsequent chlorination with phosphonyl chloridegives 5-chloro-1-methyl-3-pyrazolylcarbonyl chloride. Reduction of thechloride with sodium borohydride gives5-chloro-3-hydroxymethyl-1-methylpyrazole.

Chlorination of this product in a customary manner can give5-chloro-3-chloromethyl-1-methylpyrazole.

With regard to halogenomethyl-substituted oxazoles, chlorination ofhydroxymethyloxazole with thionyl chloride, etc., can give chloromethyloxazole. They can also be synthesized by direct ring synthesis.

For example, 5-bromomethyl-2-methyloxazole is a known compound (J. A. C.S., Vol. 104, pages 4461-4465) and 2-bromoethyl-5-ethoxycarbonyloxazoleis also a known compound (Japanese Laid-Open Patent Publication No.108771/1984).

4-Halogenomethylthiazoles can be directly synthesized, for example, byreacting dihalogenoacetones with thioacylamides such as thioacetamide(J. A. C. S., Vol. 56, pages 470-471, and ibid., Vol. 73, page 2936).

5-Halogenomethylthiazoles can be obtained by reacting a thioacylamidewith alpha-chloro-alpha-formylethyl acetate, reducing the resulting5-ethoxycarbonylthiazole with lithium aluminum hydride in a customarymanner, and halogenating the resulting 5-hydroxymethylthiazole.5-Chloromethyl-2-methylthiazole described in Zh. Obshch. Khim., Vol. 32,pages 570-575 and J. A. C. S., Vol. 104, pages 4461-4465 is a goodexample.

Reaction or thiourea instead of the thioacylamide can give2-amino-4-chloromethyl- or 2-amino-5-chloromethyl thiazole, and viadiazotization, a halogen atom, etc., can further be introduced. Thishalogen is active and can be converted to a 2-alkoxy group by a sodiumalkoxide (Japanese Laid-Open Patent Publication No. 5972/1979 and J.Chem. Soc., Perkin I, 1982, pages 159-164).

2-Halogeno-4- or 5-bromomethylthiazole can be synthesized by brominating2-halogeno-4- or 5-methylthiazoles with NBS.

The use of ammonium dithiocarbamate (Org. Synthesis, Coll. Vol. III,page 763) instead of the thioacetamide above can give 4- or5-halogenomethyl-2-mercaptothiazoles. Alkylation or haloalkylation cangive 2-alkylthio-4- or 5-halogenomethylthiazoles; or 2-substitutedalkylthio-4- or 5-halogenomethylthiazoles (J. A. C. S., Vol. 75, pages102-103).

A halogenomethyl imidazole, for example, chloromethylimidazole, can beobtained by hydroxymethylating an N-alkylimidazole with formaldehyde,optionally dealkylating it to form hydroxymethylimidazole, andchlorinating it with thionyl chloride, etc., in a customary manner(described in J. A. C. S., Vol. 71, pages 383-386).4-Hydroxymethylimidazole as one example or the hydroxymethyl imidazole,can be directly synthesized from fructose, formaldehyde and ammonia(described in Org. Synthesis Coll., Vol. III, page 460).

Hydroxymethyltriazole can be synthesized, for example, in accordancewith the procedure described in J. A. C. S., Vol. 77, pages 1538-1540,and chlorination of it can give chloromethyltriazole.

Halogenomethyloxadiazoles and halogenomethylthiazoles can be synthesizedrespectively by brominating methyl-substituted oxazole andmethyl-substituted thiazole with NBS. 3-Bromomethyl-1,2,5-thiadiazoledescribed in Japanese Laid-Open Patent Publication No. 24963/1974 and3-bromomethyl-4-chloro-1,2,5-thiadiazole are good examples thereof. Thehalogenomethyl oxadiazoles and halogenomethylthiadiazoles can besynthesized by direct ring synthesis. For example,5-chloro-3-chloromethyl-1,2,4-thiadiazole described in J. Org. Chem,Vol. 27, pages 2589-2592, 3-chloro-5-chloromethyl-1,2,4-oxadiazoledescribed in West German OLS No. 2,054,342, and5-chloromethyl-3-methyl-1,2,4-oxadiazole described in Bull. Soc. Chim.Belges., Vol. 73, pages 793-798 are good examples thereof. The2-position substituted 5-chloromethyl-1,3,4-oxa(or thia)diazoledescribed in French Patent No. 1,373,290) is another good example.

Chloromethyl-substituted heterocyclic compounds can be synthesized byreducing carboxylic acids or ester derivatives thereof with lithiumaluminum hydride, etc. to convert them to alcohol derivatives, andfurther chlorinating the alcohol derivatives with thionyl chloride, etc.As examples thereof, Japanese Laid-Open Patent Publication No.89633/1984 describes 5-chloromethyl-1,2,3-thiadiazole,4-chloromethyl-1-methyl-1,2,3,5-tetrazole and4-chloromethyl-1-methyl-1,2,3-triazole.

Halogenoalkyl-substituted, saturated or partially unsaturatedheterocyclic compounds can be converted to chloromethyl-substitutedproducts by, for example, chlorinating their alcohol derivatives in acustomary manner.

Bromomethyldioxolane and bromomethyloxothiolane can be synthesized byreacting dimethyl bromoacetal with ethylene glycol, or reacting dimethylbromoacetal with 2-mercaptoethanol or reacting an aldehyde or ketonewith epibromohydrin. For example, 2-bromomethyl-1,3-dioxolane isdescribed in Beilstein, Vol. 19, II, page 8.

As regards chloromethyl-substituted oxazoline compounds,5-chloromethyl-3-methyl-2-isoxazoline can be synthesized in accordancewith the description of Pak. J. Sci. Res., Vol. 30, pages 91-94.5-Chloromethyl-3-trifluoromethyl-2-isoxazoline may be synthesized bychlorinating 3-trifluoromethyl-5-hydroxymethyl-2-isoxazoline describedin Bull. Chem. Soc. Japan, Vol. 57, pages 2184-2187 in a customarymanner. 5-Chloromethyl-2-methyl-oxazoline is a compound described inTetrahedron, Vol. 34, pages 3537-3544.

4-Chloromethyl-2-methyl-2-thiazoline can be synthesized by chlorinating4-hydroxymethyl-2-methyl-2-thiazoline described in Heterocycles, Vol. 4,pages 1687-1692. 5-Chloromethyl-3-methyl-oxazolidin-2-one is a compounddescribed in West German OLS No. 1,932,219.3-Bromomethyl-1,1-dioxo-3-thiolene is a compound described in U.S. Pat.No. 4,561,764 and can be synthesized by bromination with NBS.

5-Pyrimidinylmethyl alcohol is obtained from 5-pyrimidinecarbaldehyde,and 2-chloro-5-pyrimidinylmethyl alcohol, from2-chloro-5-pyrimidinecarbaldehyde. 3-Pyridazinylmethyl alcohol can besynthesized from furfuryl acetate (Acta Chem. Scand., vol. 1, page 619).With regard to pyrazinyl alkyl halides, methylpyrazine ordimethylpyrazine which is easily available can be converted tochloromethylpyrazine by using N-chlorosuccinimide (Synthesis, 1984,pages 676-679). This reaction can be applied to methylpyrazines havingother substituents and halo-substituted methylpyridazines such as3-chloro-6-methylpyridazine (described in J. Chem. Soc., 1947, page242), and by this reaction 3-chloro-6-pyridazinylmethyl chloride can besynthesized. Furthermore, 2-chloro-5-pyrimidinylmethyl bromide can beobtained from 2-chloro-5-methylpyrimidine (Reacts. Sposobnost. Org.Soedin., vol. 5, pages 824-837) and N-bromosuccinimide.

As described in J. Hetrocycl. Chem., vol. 19, page 407 and Chem. Pharm.Bull., vol. 28, pages 3057 and 3063, ethyl2-chloropyrazine-5-carboxylate can be synthesized, and reduced to thecorresponding methanol 2,910,824).

As regards triazinyl alkyl halides, 2,5-triazin-2-ylmethyl chloride, forexample, can be obtained by reacting 2-methyl-1,3,5-triazine withN-chlorosuccinimide (J. Org. Chem., vol. 29, pages 1527-1537).3,5-Dichloro-6-methyl-1,2,4-triazine (described in J. Med. Chem., vol.10, pages 883-887) and 3-chloro-6-methyl-1,2,4,5-tetrazine (J. Org.Chem., vol. 46, pages 5102-5109) can be chlorinated similarly byreaction with N-chlorosuccinimide.

In the formula (I) in which X is

or Y is

and which can be obtained by the above process (a), (b), (c), (d), (e)or (f), each hydrogen atom of the

group and the

group thereof may be substituted by or added to other groups.

As specific examples, some compounds having active olefinic linkage,such as methylvinylketone, ethylacrylate, and acrylonitrile can bereacted with the ═CH— group by Michael type addition. (see JapaneseLaid-Open Patent Application No. 151,882/1975).

Moreover, by Mannich reaction and others similar thereto, specifically,a dialkylaminomethyl group can be introduced to α-carbon atom of thenitromethylene group, and also active aldehydes such as formaldehyde andchloral may be added as well. (see Japanese Laid-Open Patent ApplicationNo. 151,882/1975).

In addition, each hydrogen atom of the above

group and

group can also be halogenated by a halogenating agent such asN-chlorosuccinimide, N-bromosuccinimide, perchloryl fluoride and halogenper se. (see U.S. Pat. Nos. 3,933,809 and 3,962,233, Japanese Laid-OpenPatent Application No. 54,532/1974).

In the above cases, the formula (I) may have the following formula:

wherein

n, R¹, R², R³, R⁴, R⁵, R⁶, R, Z and Hal have the same meanings as statedabove, and

L represents a halogen atom, a phenylthio group or an alkoxycarbonylgroup.

Glyoxalic acid and dimethylformaldehydedimethylacetal can also bereacted with α-carbon atom of the nitromethylene group, and said formula(I) may have the following formula:

wherein n, R¹, R², R³, R⁴, R⁵ R⁶ R and Z have the same meanings asstated above.

The nitrogen atom of the above

group and α-carbon atom of the nitromethylene group can independently beacylated, sulfenylated or sulfonylated. (see Netherland Patent No.7,306,145, U.S. Pat. Nos. 3,985,736, 3,996,372, 4,020,061, 4,022,775,4,052,411, 4,053,662 and 4,076,813).

Acylisocyanates and sulfonylisocyanates can be reacted with α-carbonatom of the nitromethylene group. (see U.S. Pat. Nos. 4,013,766,4,025,634, 4,029,791 and 4,034,091).

The nitrogen atom of the above

group can also be alkylated (see Belgian Patent No. 821,282) and byusing said reaction, third-position of the imidazolidines or thetetrahydropyrimidines can be alkylated to obtain the correspondingformula (I).

In carrying out the process (a), suitable diluents may be all inertorganic solvents.

Examples of such diluents include water; aliphatic, alicyclic andaromatic hydrocarbons (which may optionally be chlorinated) such ashexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene,methylene chloride, chloroform, carbon tetrachloride, ethylene chloride,trichloroethylene and chlorobenzene; ethers such as diethyl ether,methyl ethyl ether, diisopropyl ether, dibutyl ether, propylene oxide,dioxane and tetrahydrofuran; nitriles such as acetonitrile,propionitrile and acrylonitrile; alcohols such as methanol, ethanol,isopropanol, butanol and ethylene glycol; acid amides such asdimethylformamide and dimethylacetamide; sulfones and sulfoxides such asdimethyl sulfoxide and sulfolane; and bases such as pyridine.

The process (a) can be carried out over a wide temperature range.Generally, it can be carried out at a temperature between about −20° C.and the boiling point of the mixture, preferably between about 50° C.and about 120° C. Desirably, the reaction is carried out under normalatmospheric pressure, but it is also possible to operate under elevatedor reduced pressures.

In the process (a), the desired novel compounds of the formula (I) canbe obtained, for example, by reacting the compounds of the formula (II)with 1 to about 1.2 moles, preferably 1 to about 1.1 moles, per mole ofthe compounds of the formula (II), of the compounds of the formula (III)in an inert solvent such as an alcohol (e.g., methanol or ethanol) untilthe generation of mercaptan ceases.

In carrying out the processes (b) and (c), suitable diluents may be theabove inert solvents exemplified for the process (a). As the base, forexample, hydroxides, carbonates, bicarbonates and alcoholates of alkalimetals, and testiary amines such as triethylamine, diethylamine andpyridine may also be cited.

The processes (b) and (c) can be carried out over a broad temperaturerange, generally between about −20° C. and the boiling point of themixture, preferably between about 0° C. and about 50° C.

The reaction is carried out preferably under normal atomosphericpressure, but it is also possible to perform it under elevated orreduced pressure.

In the above processes (b) and (c), for example, about 1 to about 5moles preferably about 2 to about 4 moles, of a base and about 0.9 toabout 4 moles preferably about 1 to about 3 moles, of the compounds ofthe formulae (IV) or (V) can be used, per mole of the compounds of theformula (II).

In carrying out process (d), suitable diluents may be the above inertsolvents exemplified for the process (a).

According to process (d), the desired compounds of the formula (I) canbe easily obtained, for example, by reacting 1 mole of the compounds ofthe formula (II) with 1 to about 1.2 moles, preferably 1 to about 1.1moles, of nitroguanidine under heat in a water solvent.

The process (b) can be carried out at a temperature of, for example,about 0° C. to about 100° C., preferably about 30° C. to about 80° C.The reaction is preferably carried out under normal atmosphericpressure, but can also be carried out under elevated or reducedpressures.

In the practice of process (e), the compounds of the formula (VI) isusually dissolved in an acid such as conc. sulfuric acid prior to thereaction.

In carrying out the processes, the compounds of the formula (VI) andfuming nitric acid (with a purity of at least 98%) are reacted at lowtemperatures, preferably about 0° C. or lower to obtain the desiredcompounds of the formula (I) (by applying the method of British PatentApplication No. 2,055,796).

The compound of general formula (VI) used in the above process isgenerally present in the form of a hydrohalide as a result of itssynthesis as stated above, and usually it is neutralized in a customarymanner before using it in the process (e).

In the practice of the process (f), suitable diluents may be the aboveinert organic solvents exemplified for the process (a). As the bases,for example, hydrides such as sodium hydride and potassium hydride,hydroxides and carbonates of alkali metals may also be cited.

The process (f) can be carried out over a broad temperature range,generally between about 0° C. and about 100° C., preferably betweenabout 10° C. and about 80° C.

The reaction (f) is carried out preferably under normal atmosphericpressure, but it is also possible to perform it under elevated orreduced pressure.

In the process (f), the desired compounds of the formula (I) can beobtained, for example, by reacting the compounds of the formula (VII),in the presence of about 1.1 to 1.2 moles, per mole of the compound(VII), of sodium hydride as a base, with 1 to about 1.2 moles preferably1 to about 1.1 moles, per mole of the compound (VII), of the compoundsof the formula (VIII) in an inert solvent such as dimethylformamide. Inthe process (f), it is preferable for the reaction that the compound ofgeneral formula (VII) be converted in advance into its sodium salt byusing sodium hydride. In view of the characteristics of sodium hydride,such a reaction is desirably carried out under a nitrogen gasatmosphere.

The compounds of the formula (I) in accordance with this inventioninclude a tautomer as shown by the following formula.

In the case of X being NH and Y being CH,

In addition, where Y is C—R⁹, the corresponding formula (I) may includeE,Z-isomer.

The compounds of the formula (I) may also be present in the form of asalt. Examples of the salt are inorganic acid salts, sulfonate salts,organic acid salts and metal salts.

The active compounds according to the invention exhibit powerfulinsecticidal effects.

They can, therefore, be used as insecticides. The active compounds canbe used for control and eradication of a wide range of pests, includingsucking insects, bitting insects and other plant parasites, pests onstored grains and pests causing health hazards.

Examples of the pests are shown below.

Coleopterous insects

Callosobruchus chinensis,

Sitophilus zeamais,

Tribolium castaneus,

Epilachna vigitoctomaculata,

Agriotes fuscicollis,

Anomala rufocuprea,

Leptinotarsa decemkineata,

Diabrotica spp.,

Monochamus alternatus,

Lissorhoptrus oryzophilus, and

Lyctus brunneus.

Lepidopterous insects

Lymantria dispar,

Malacosoma neustria,

Pieris rapae,

Spodoptera litura,

Mamestra brssicae,

Chilo suppressalis,

Pyrausta nubilalis,

Ephestia cautella,

Adoxophyes orana,

Carpocapsa pomonella,

Agrotis fucosa,

Galleria mellonella,

Plutella maculipennis, and

Phyllocnistis citrella.

Hemipterous insects

Nephotettix cincticeps,

Nilaparvata lugens,

Pseudococcus cometocki,

Unaspis yanonensis,

Myzus persicae,

Aphis pomi,

Aphis gossypii,

Rhopalosiphum pseudobrassicas,

Stephanitis nashi,

Nazara spp.,

Cimex lectularius,

Trialeurodes vaporariorum, and

Psylla spp.

Orthopterous insects

Blatella germanica,

Periplaneta americana,

Cryllotalpa africana, and

Locusta migratoria migratoriodes.

Isopterous insects

Deucotermes speratus, and

Coptotermes formosanus.

Dipterous insects

Musca domestica,

Aedes aegypti,

Hylemia platura,

Culex pipens,

Anopheles sinensis, and

Culex tritaeniorhynchus.

In the field of veterinary medicine, the novel compounds of thisinvention are effective against various noxious animal parasites (endo-and ecto-parasites) such as insects and worms. Examples of such animalparasites are shown below.

Insects

Gastrophilus spp.,

Stomoxys spp.,

Trichodectes spp.,

Rhodnium spp., and

Ctenocephalides canis.

Substances having pesticidal activity against all of these pests maysometimes be referred to in this application simply as insecticides.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, natural and synthetic materials impregnated withactive compound, very fine capsules in polymeric substances, coatingcompositions for use on seed, and formulations used with burningequipment, such as fumigating cartridges, fumigating cans and fumigatingcoils, as well as ULV cold mist and warm mist formulations.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid solvents diluents or carriers, there are suitable in the main,aromatic hydrocarbons, such as xylene, toluene or alkyl napthalenes,chlorinated aromatic or chlorinated aliphatic hydrocarbons, such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example mineral oilfractions, alcohols, such as butanol or glycol as well as their ethersand esters, ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, or strongly polar solvents, such asdimethylformamide and dimethyl-sulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for exampleaerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, corn cobs acid tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulation.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 per cent by weight ofactive compound, preferably from 0.5 to 90 per cent by weight.

The active compounds according to the invention can be present in theircommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, baits, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphates, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas, substances produced by microorganisms.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agent are compounds which increase the action of theactive compounds, without it being necessary for the synergistic agentadded to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to100% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

The following examples illustrate the present invention specifically. Itshould be noted, however, that the invention is not limited to themalone.

Preparative Examples EXAMPLE 1

A mixture of N-(2-chloro-5-pyridylmethyl)3-aminopropanethiol (4.3 g),1-nitro-2,2-bis(methylthio)ethylene (3.3 g) and ethanol (40 ml) washeated under reflux for 10 hours in a stream of nitrogen. After thereaction, about ⅔ of ethanol was distilled off under reduced pressure.Ether was added little by little to the reaction mixture to precipitatecrystals. The crystals were collected by filtration, and washed with amixture of ethanol and ether to give the desired3-(2-chloro-5-pyridymethyl)-2-nitromethylenetetrahydro-2H-1,3-thiazine(1.3 g) as yellow crystals.

m.p. 164-166° C.

EXAMPLE 2

2-Nitromethylenethiazolidine (2.9 g) was dissolved in dry acetonitrile(30 ml), and 60% sodium hydride (0.9 g) was added at room temperature ina stream of nitrogen. Subsequently, the mixture was stirred at roomtemperature until the generation of hydrogen ceased. Then, a solution of2-chloro-5-pyridylmethyl chloride (3.2 g) in dry acetonitrile (5 ml) wasadded at room temperature, and the mixture was stirred at roomtemperature for 1 day. Acetonitrile was then distilled off under reducedpressure, and dichloromethane was added to the residue. The mixture wasthen washed with water. Dichloromethane was distilled off from thedichloromethane layer. The remaining oil was purified by silica gelcolumn chromatography to give the desired3-(2-chloro-5-pyridylmethyl)-2nitromethylenethiazolidine (1.6 g).

mp. 177-179° C.

EXAMPLE 3

A mixture of N-(3-pyridylmethyl)3-aminopropanethiol (1.8 g),1-nitro-2,2-bis(methylthio)ethylene (1.7 g) and ethanol (40 ml) washeated under reflux for 5 hours under a nitrogen stream. After thereaction, about ⅔ by volume of ethanol was distilled off under reducedpressure. Ether was added little by little to the reaction mixture toprecipitate crystals. The crystals were collected by filtration, andwashed with a mixture of ethanol and ether to give the desired3-(3-pyridylmethyl)2-nitromethylenetetrahydro-2H-1,3-thiazine (1.2 g).

mp. 143-146° C.

EXAMPLE 4

2-Nitromethylenethiazolidine (2.9 g) was suspended in dry acetonitrile(30 ml), and 60% sodium hydride (0.9 g) was added under a nitrogenstream. Then, the mixture was stirred at room temperature until thegeneration of hydrogen ceased. A solution of 3-picolyl chloride (3.2 g)in dry acetonitrile (5 ml) was added, and the mixture was stirred atroom temperature for 3 hours. Acetonitrile was distilled off underreduced pressure. Dichloromethane was added to the residue; and themixture was washed with water. Dichloromethane was then distilled offfrom the dichloromethane layer. The remaining oily product was purifiedby column chromatography to give the desired3-(3-pyridylmethyl)2-nitromethylenethiazolidine (0.5 g).

mp. 96-100° C.

EXAMPLE 5

A mixture of 16.8 g ofN-(1-methyl-4-pyrazolylmethyl)-trimethylenediamine, 16.5 g of1-nitro-2,2-bis(methylthio)ethylene and 200 ml of ethanol was heatedunder reflux until the generation of methylmercaptan ceased. The mixturewas cooled, and the precipitated crystals were collected by filtration.Washing with methanol gave 16.6 g of the desired1-(1-methyl-4-pyrazolylmethyl)2-(nitromethylene)tetrahydropyrimidine aspale yellow crystals.

mp. 186-190° C.

EXAMPLE 6

A mixture of 15.5 g of N-(3-methyl-5-isoxazolylmethyl)-ethylenediamine,16.5 g of 1-nitro-2,2-bis(methylthio)ethylene and 200 ml of ethanol washeated under reflux until the generation of methylmercaptan ceased. Theperiod of about 3 hours was required. Then, the reaction mixture wascooled to room temperature, whereupon the desired product precipitatedas crystals. The crystals were collected by filtration and washed withethanol to give 12.5 g of1-(3-methyl-5-isoxazolylmethyl)2-(nitromethylene)imidazolidine as yellowcrystals.

mp. 168-170° C.

EXAMPLE 7

2-Nitromethylene imidazolidine (12.9 g) was dissolved in 60 ml of drydimethylformamide, and 4.4 g of 60% sodium hydride was added little bylittle in a nitrogen stream at room temperature, and successively, themixture was started at room temperature to 30° C. for 3 hours to formthe sodium salt of the imidazolidine compound. Then, 11.8 g of5-isoxazolylmethyl chloride was added at room temperature, and themixture was stirred at room temperature for 24 hrs. The reaction mixturewas carefully poured into 150 ml of ice water and extracted twice withdichloromethane. Dichloromethane was distilled off from thedichoromethane layers to give 12 g of the desired1-(5-isoxazolylmethyl)2-(nitromethylene)imidazolidine as brown crystals.

mp. 156-158° C.

EXAMPLE 8

N-(2-Methyl-5-thiazolylmethyl)trimethylenediamine (18.5 g) was dissolvedin 100 ml of acetonitrile, and 1-nitro-2,2-bis(methylthiio)ethylene(16.5 g) was added. With stirring, the mixture was refluxed for 6 hours.After the reaction, the reaction mixture was cooled to room temperature.The resulting crystals were collected by filtration and washed withmethanol to give 10.2 g of the desired1-(2-methyl-5-thiazolylmethyl)2-(nitromethylene)tetrahydropyrimidine.

mp. 204-207° C.

EXAMPLE 9

A mixture of 2-fluoro-5-pyridylmethyl bromide (9.5 g),2-(nitroimino)imidazolidine (6.5 g), potassium carbonate (7.6 g) andacetonitrile (100 ml) was refluxed for 2 hours with stirring. After thereaction, the reaction mixture was cooled to room temperature, and coldwater (100 ml) was added. The resulting crystals were collected byfiltration and washed with ether to give slightly colored1-(2-fluoro-5-pyridylmethyl)-2-(nitroimino)imidazolidine (6.0 g) as thedesired compound.

mp. 121-124° C.

EXAMPLE 10

A solution composed of N-(2-chloro-5-pyridylmethyl)-trimethylenediamine(10 g), nitroguanidine (5.7 g) and water (80 ml) was heated at 80° C.for 3 hours. The reaction mixture was cooled to room temperature, andextracted twice with 50 ml of dichloromethane. Dichloromethane wasdistilled off from the extracts, and the tarry residue was purified bysilica gel column chromatography to give almost colorless1-(2-chloro-5-pyridylmethyl)-2-(nitroimino)tetrahydropyrimidine (6.1 g).

mp. 113-117° C.

EXAMPLE 11-i

A solution of N-(2-chloro-5-pyridylmethyl)ethylenediamine (18.6 g) intoluene (200 ml) was stirred at room temperature, and cyanogen bromide(10.6 g) was added portionwise. Then, the mixture was further stirrred.Since the desired 1-(2-chloro-5-pyridylmethyl)-2-iminoimidazolidineprecipitated as a hydrobromide, the reaction mixture was filtered andthe filtrate was washed with ether.

mp. 202-205° C.

EXAMPLE 11-ii

The hydrobromide (5.8 g) synthesized in Example 11-i was added to 98%sulfuric acid (30 ml) at 0° C. Then, with stirring, 2 ml of fumingnitric acid was added dropwise at 0° C. After the addition, the mixturewas stirred at 0° C. for 2 hours. The reaction mixture was poured intoice water (100 g) and extracted with dichloromethane. Dichloromethanewas distilled off from the extract under reduced pressure to give paleyellow crystals. The crystals were washed with ether to give1-(2-chloro-5-pyridylmethyl)-2-(nitroimino)imidazolidine (1.5 g).

mp. 136-139° C.

EXAMPLE 12

Sodium hydride (0.48 g) was added to a solution of2,2,2-trifluoroethanol (2.4 g) in toluene (30 ml) was added, and themixture was stirred until the generation of hydrogen ceased. As aresult, 2,2,2-trifluoroethanol sodium salt was prepared. To the productwere added 1-(2-chloro-5-pyridylmethyl)-2-(nitroimino)imidazolidine (5.1g) synthesized by the method of Example 3 and a catalytic amount of4-dimethylaminopyridine. The mixture was heated at 80° C. for 10 hourswith stirring. After cooling the reaction mixture, the precipitatedcrystals were collected by filtration, washed with water and ether andthen purified by silica gel chromatography to give1-[2-(2,2,2-trifluoroethoxy)-5-pyridylmethyl]-2-(nitroimino)imidazolidine(1.5 g).

mp. 109-112° C.

EXAMPLE 13

A mixture of N-(5-pyrimidinylmethyl)ethylenediamine (15.2 g),1-nitro-2,2-bis(methylthio)ethylene (14.9 g) and ethanol (100 g) wasrefluxed with stirring until the generation of methylmercaptan ceased(for about 3 hours). The reaction mixture was cooled to roomtemperature, and the resultant crystals were collected by filtration.The crystals were washed with ethanol, and dried to give1-(5-pyriminidinylmethyl)-2-(nitromethylene)imidazolidine (12.7 g) aspale yellow crystals. This product decomposes at 236° C.

EXAMPLE 14

2-Nitromethyleneimidazolidine (12.9 g) was dissolved in drydimethylformamide (100 ml), and at room temperature 60% oily soldiumhydride (4.4 g) was added. The mixture was stirred at room temperatureuntil the generation of hydrogen ceased. Then,2-methyl-5-pyrazinylmethyl chloride (14.3 g) was added at roomtemperature, and the mixture was stirred at 40° C. for 8 hours. Aftercooling to room temperature, the reaction mixture was added to 200 ml ofwater, and extracted with dichloromethane. On distilling offdichloromethane from the organic layer under reduced pressure,1-(2-methyl-5-pyrazinylmethyl)-2-(nitromethylene)imidazolidine (5.4 g)was obtained as yellow crystals having a melting point of 163 to 166° C.

EXAMPLE 15

A mixture of 2 g of 2-amino-1-(2-chloro-5-pyridylmethylamino)propane,1.6 g of 1-nitro-2,2-bis(methylthio)ethylene and 20 ml of methanol wasrefluxed for 5 hours with stirring. A crystaline product wasprecipitated after standing at room temperature. The product wasfiltered with suction, washed with methanol and then dried in vacuum.1.9 g of1-(2-chloro-5-pyridylmethyl)-4-methyl-2-(nitromethylene)imidazolidinewas obtained in form of light yellow crystals.

mp. 170-174° C.

EXAMPLE 16

A mixture of 2.6 g ofN-(3-methyl-5-isoxazolylmethyl)-N′-(1-methyl-4-pyrazolylmethyl)trimethylenediamine,1.6 g of 1-nitro 2,2-bis(methylthio)ethylene and 10 ml of ethanol wasrefluxed for 15 hours with stirring. After the reaction, the ethanol wasremoved by vacuum distillation. The tarry residue was purified bychromatography on a silicagel column. The product, 0.7 g of1-(3-methyl-5-isoxazolylmethyl-3-(1-methyl-4-pyrazolylmethyl)-2-(nitromethylene)tetrahydropyrimidinewas obtained as a viscous oil.

n_(D) ²⁰1.5670

EXAMPLE 17

6.6 g of finely powdered 1-nitro-2,2-bis(methylthio)ethylene was wellmixed with 7.5 g of 2-(2-chloro-5-pyridylmethylamino)ethanol. Themixture was heated to 110-120° C. for 30 minutes or until the generationof methylmercaptan is ceased. The resulting oil was cooled to roomtemperature and purified by chromatography on a silicagel column. Theproduct, 3-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)oxazolidineweighed 1.7 g.

mp. 123-124° C.

EXAMPLE 18

2.6 g of potassium hydroxide was dissolved in 20 ml of anhydrousethanol. To the solution, were added 3.7 g of2-(2-methyl-5-pyrazinylmethylamino)ethanethiol under nitrogenatmosphere. The solution was then cooled to 0° C., and 3.0 g of2,2-dichloro-1-nitroethylene was added dropwise at 0-10° C. After theaddition, the mixture was stirred for 1 hour at 10° C. The ethanol wasremoved by vacuum distillation, chloroform was added to the residue andthe chloroform layer was washed with 1% of sodium hydroxide solution andwater. The chloroform layer was treated by usual manner, light yellowcrystals of3-(2-methyl-5-pyrazinylmethyl)-2-(nitromethylene)thiazolidine wereobtained, and weighed 2.0 g.

mp. 147-150° C.

EXAMPLE 19

A mixture of 4.7 g of N-(1,2,5-thiadiazol-3-ylmethyl)ethylenediamine,3.4 g of nitroguanidine and 20 ml of water was stirred at 50-60° C. for1 hour then at 70° C. for 20 minutes. The resulting solution was thencooled slowly to 5° C., and the product was precipitated. Thecrystalline product was collected by filtration washed with water andmethanol, and dried. The yield of1-(1,2,5-thiadiazol-3-ylmethyl)-2-(nitroimino)imidazolidine was 2.9 g.

mp. 162-165° C.

EXAMPLE 20

A mixture of 2.9 g of 2-nitroiminothiazolidine, 2.9 g of anhydrouspotassium carbonate, 3.2 g of 2-chloro-5-pyridylmethylchloride and 50 mlof acetonitrile was refluxed for 5 hours with vigorously stirring. Afterthe reaction, most of the acetonitrile was removed by distillation andwater was added to the residue. As the solid product was separated, itwas collected by filtration. The crude material was recrystallized fromethanol to give desired3-(2-chloro-5-pyridylmethyl)-2-(nitroimino)thiazolidine.

yield 3.8 g

mp. 137-138° C.

EXAMPLE 21

To a mixture of 1.3 g of finely powdered 2-nitroiminoimidazolidine and30 ml of dry acetonitrile was added portionwise 0.4 g of sodium hydride(60% in oil) at room temperature and was stirred until the generation ofhydrogen gas ceased. A solution of 1.7 g of2-chloro-5-thiazolylmethylchloride in 10 ml of acetonitrile was thenadded dropwise at room temperature. After the addition, the mixture wasstirred for 3 hours at room temperature and poured onto ice water. Theorganic layer was extracted with dichloromethane and the dichloromethaneextract was washed with 1% sodium hydroxide solution and water. Theproduct was solidified after evaporation of dichloromethane, washed withether and dried. The desired1-(2-chloro-5-thiazolylmethyl)-2-(nitroimino)imidazolidine weighed 1.4g.

mp. 147-150° C.

EXAMPLE 22

By the procedure described in example 7 gummy substance was obtainedfrom 2.3 g of ethyl nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetateand 1.6 g of 2-chloro-5-pyridylmethylchloride. This was triturated inethanol and insoluble material was washed with hexane, then was purifiedby chromatography on a silicagel column. The desired ethyl[3-(2-chloro-5-pyridylmethyl)tetrahydro-2H-1,3-thiazin-2-ylidene]acetateweighed 0.2 g.

mp. 180-184° C.

EXAMPLE 23

5.8 g of 2-imino-3-(4-pyridylmethyl)thiazolidine was added to 20 ml ofconc. sulfuric acid at −5˜0° C. 6 ml of fuming nitric acid was thenadded dropwise to the solution at the same temperature. After stirringfor 30 minutes at 0˜5° C., the reaction mixture was poured onto crushedice. Twice extract with dichloromethan followed by treating in the usualway yielded 1.4 g of desired2-nitroimino-3-(4-pyridylmethyl)thiazolidine.

EXAMPLE 24

A mixture of 2.7 g of3-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)thiazolidine, 3.5 g ofmethyl vinylketone and 30 ml of chloroform was stirred for 2 days at 40°C. under nitrogen atmosphere. 3.5 g of methyl vinylketone was then addedto the reaction mixture and stirred again for 2 days at the sametemperature. After volatile material was removed in vacuum, the residuewas purified by chromatography on silicagel column. The desired3-(2-chloro-5-pyridylmethyl)-2-(1-nitro-4-oxopentylidene)thiazolidineweighed 0.1 g.

mp. 75-80° C.

EXAMPLE 25

A mixture of 2.3 g of1-(4-pyridylmethyl)-2-nitromethylene)tetrahydropyrimidine, 0.5 g ofparoformaldehyde and 30 ml of dioxane was vigorously stirrred for 2hours at 70-80° C. After the reaction, the dioxane was evaporated toabout one third of its volume under reduced pressure. The crystallizedproduct was filtered and dried. The yield of desiredbis-[α-nitro-1-(4-pyridylmethyl)tetrahydropyrimidin-2-ylidenemethyl]methane was 1.8 g.

mp. 222-223° C.

EXAMPLE 26

To a solution of 2.4 g of1-(3-methyl-5-isoxazolylmethyl)-2-(nitromethylene)tetrahydropyrimidineand 30 ml of dry dichloromethane was added 1.6 g oftrichloroacetaldehyde at room temperature. After stirring for 3 hours at25-30° C., crystallized product was filtered, washed with ether anddried. The desired1-(3-methyl-5-isoxazolylmethyl)-2-(1-nitro-2-hydroxy-3,3,3-trichloropropylidene)tetrahydropyrimidineweighed 3.1 g.

mp. 128-130° C. (decomp.)

EXAMPLE 27

2.5 g of 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)imidazolidinewas dissolved in 40 ml of dry dichloromethane and 10 ml of water wasadded. A solution of 1.6 g of bromine in 10 ml of dichloromethane wasadded to the mixture within 10 minutes at 0-5° C. with stirring. Afterstirring for 10 minutes at 0-5° C., crystallized product was filtered,washed with cold water and a small quantity of dichloromethane anddried. The yield of1-(2-chloro-5-pyridylmethyl)-2-(bromonitromethylene)imidazolidine was2.5 g.

mp. 110-115° C. (decomp.)

EXAMPLE 28

To a mixture of 1.2 g of finely powdered1-(4-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine in 20 ml ofmethanol was added 2 drops of conc. sulfuric acid and then 1.6 g of 25%aqueous glyoxylic acid. The mixture was stirred for 3 hours at roomtemperature. After adjusting to pH 7, the precipitated product wasfiltered, washed with water, methanol and ether respectively and dried.The desired3-[1-(4-pyridylmethyl)-1H,4H,5H,6H-tetrahydropyrimidin-4-yl]-3-nitroacrylic acid weighed 1.1 g.

mp. 150-155° C. (decomp.)

EXAMPLE 29

3.1 g of phenylchloroformate was added to a solution of 1.6 g of1-methylimidazole in 50 ml of dichloromethane below 0° C. After stirringfor 30 minutes at the same temperature, 2.5 g of1-(2-chloro-5-pyridylmethyl)-(2-nitromrethylene)imidazolidine was addedto the mixture and the resulting mixture was stirred for 24 hours atroom temperature. The mixture then washed with water, 1% hydrochloricacid and 1% sodium hydroxide solution respectively. Removing thedichloromethane by distillation gives glassy phenylnitro{1-(2-choro-5-pyridylmethyl)-3-phenoxycarboylimidazolidin-2-ylidene}acetate(3.2 g). This was then dissolved in 20 ml of dimethylformamide, 1.7 g ofsodium carbonate was added to the solution, and the mixture was stirredfor 3 days at room temperature. Water was then added and the organiclayer was extracted with dichloromethane. The extract was washed with 1%sodium hydroxide solution and water. After evaporation ofdichloromethane, the residue was purified by chromatography on asilicagel column. The desired product, phenylnitro-{1-(2-chloro-5-pyridylmethyl)imidazolidin-2-ylidene}acetateweighed 0.2 g. mp. 224-228° C. (decomp.)

EXAMPLE 30

0.2 g of sodium hydride 60% in oil was added to a solution of 1.1 g of1-(3-methylisoxazol-5-ylmethyl)-2-nitroiminoimidazolidine in 15 ml ofdry dimethylformamide and the mixture was stirred until the generationof hydrogen gas ceased. 1.2 g of 2-methyl-5-nitrobenzenesulfonylchloridewas then added to the mixture. After stirring for 1 day at roomtemperature, the reaction mixture was poured into ice water, and theorganic layer was extracted with dichloromethane. The dichloromethanewas removed by distillation to give crystalline product, and this waswashed with ether. The desired1-(2-methyl-5-nitrobenzenesulfonyl)-3-(3-methylisoxazol-5-ylmethyl)-2-nitroiminoimidazolidineweighed 1.1 g.

mp. 154-156° C.

EXAMPLE 31

0.2 g of sodium hydride 60% in oil was added to a solution of 1.3 g of1-(2-chloro-5-pyridylmethyl)-2-nitromethyleneimidazolidine in 15 ml ofdry dimethylformamide, and the mixture was stirred at room temperatureuntil the generation of hydrogen gas ceased. 0.9 g of4-chlorobenzenesulfenylchloride was then drop into the solution at 0° C.with stirring. After stirring for 1 hour at room temperature, thereaction mixture was poured into ice water. The precipitated crystal wasfiltered and recrystalized from ethyl acetate to give1-(2-chloro-5-pyridylmethyl)-2-{(4-chlorophenylthio)nitromethylene}imidazolidine.The yield was 1.3 g.

mp. 159-161° C.

EXAMPLE 32

A solution of 0.9 g of benzenesulfonylisocyanate in 10 ml of drydichloromethane was added dropwise to a solution of 1.3 g of1-(2-chloro-5-pyridylmethyl)-2-nitromethyleneimidazolidine in 25 ml ofdry dichloromethane at room temperature. The solution was stirred for 2hours at the same temperature and then about a half volume ofdichloromethane was evaporated under reduced pressure. The product whichcrystallized was filtered and washed with ether. The desiredN-benzenesulfonyl-2-{1-(2-chloro-5-pyridylmethyl)imidazolidin-2-ylidene}-2-nitroacetamideweighed 1 g.

mp. 95-100° C.

EXAMPLE 33

A mixture of 2.2 g of 2-nitroimino-1-(3-pyridylmethyl)imidazolidine, 1.6g of 2-chloro-5-chloromethylpyridine, 1.4 g of anhydrous potassiumcarbonate in 30 ml of acetonitrile was refluxed for 16 hours withstirring. The acetonitrile was then removed under reduced pressure,dichloromethane was added to the residue and was washed with water and1% sodium hydroxide solution. The residue after removing dichloromethaneunder reduced pressure was purified by chromatography on a silicagelcolumn to give1-(2-chloro-5-pyridylmethyl-2-nitroimino-3-(3-pyridylmethyl)imidazolidine.The yield was 2.1 g.

mp. 143-144° C.

EXAMPLE 34

0.4 g of sodium hydride 60% in oil was added portionwise to a solutionof 2.6 g of 1-(2-chloro-5-pyridylmethyl)-2-nitroiminoimidazolidine in 20ml of dry dimethylformamide. The mixture was stirred at room temperatureuntil the evolution of hydrogen ceased. A solution of 1.5 g of isopropylbromide in 5 ml of dry dimethylformamide was added dropwise to themixture at room temperature and stirred for 3 hours at room temperatureafter the addition. The reaction mixture was then poured into ice water,and the precipitated crystals filtered. This was recrystallized fromethanol to give1-(2-chloro-5-pyridylmethyl)-3-isopropyl-2-nitroiminoimidazolidine. Theyield was 1.5 g.

mp. 138-142° C.

EXAMPLE 35

A mixture of 2.7 g of3-(2-chloro-5-pyridylmethyl)-2-nitromethylenethiazolidine and 8 ml ofbutyric anhydride was stirred for 8 hours at 60° C. under nitrogenatmosphere. The volatile material was then removed by distillation at 1mmHg, keeping the bath temperature below 60° C. The residue wasdissolved in dichloromethane and washed with 1% sodium hydroxidesolution. The dichloromethane layer was then purified by chromatographyon a silicagel column to give viscous oily1-{3-(2-chloro-5-pyridylmethyl)thiazolidine-2-ylidene}-1-nitro-2-pentanone.The yield was 0.15 g.

n_(D) ²⁰1.6342

In accordance with the same method as in the above examples, thecompounds of the formula (I) are shown in the following tables.

In the tables, “—” for R³ and R⁴ means n is 0 and in such case, thecorresponding ring-structure is 5-membered heterocyclic ring.

The case where X is a sulfur atom and the formula (I) represents thefollowing formula:—(table 1)

TABLE 1

Bonding positions Compound of the No. m R pyridine ring Q_(l) 36 2 H 5-2-F 37 3 H 5- 2-F 38 2 —CH₃ 5- 2-Cl 39 2 H 5- 2-Br 40 2 H 5- 2,3-Cl₂ 412 H 5- 2,3,4,6-F₄ 42 2 H 4- 2-Cl 43 3 H 5- 2-Br 44 2 H 5- 2-F, 3-Cl 45 2H 2- 3-Cl 46 3 H 2- 5-Cl 47 2 H 2- 3,5-Cl₂ 48 3 H 2- 5-F 49 2 H 2- 6-Br50 3 H 3- 2-Cl 51 3 H 3- 5-Cl 52 2 H 3- 5-Br 53 2 H 3- 5-F 54 2 —CH₃ 5-2-F 55 3 H 5- 2,4-Cl₂ 56 2 H 5- 2,4-Br₂ 57 2 H 4- 2,6-F₂ 58 3 H 4- 2-F59 2 H 4- 2,6-Br₂ 60 2 H 5- 2-F, 3-Br 61 2 H 5- 2-Cl, 3-F 62 2 —C₂H₅ 5-2-Cl₃ 63 2 H 4- — 64 3 H 4- — 65 2 H 5- 2-CH₃ 66 3 H 5- 2-CH₃ 67 2 H 5-2-C₂H₅ 68 2 H 5- 2-CH₂CH═CH₂ 69 2 H 5- 2-CH₂C≡CH 70 3 H 5- 2-OCH₃ 71 2 H5- 2-SCH₃ 72 2 H 5-

73 2 H 5- 2-Cl, 3-CH₃ 74 2 —CH₃ 3- — 75 2 H 5- 2-CF₃ 76 3 H 5- 2-CF₃ 772 H 5- 2-NO₂ 78 3 H 5- 2-NO₂ 79 2 H 5- 2-CN 80 3 H 5- 2-CN 81 2 H 5-

82 2 H 5-

83 2 H 5-

84 3 H 5-

85 2 H 5- 2-CCl₃ 86 3 H 5- 2-C₂H₄OC₂H₅ 87 2 H 5- 2-CH₂OCH₃ 88 2 H 5-2-OCHF₂ 89 2 H 5- 2-OCF₃ 90 2 H 5- 2-OCH₂CF₃ 91 3 H 5- 2-SCClF₂ 92 2 H5- 2-SCF₃ 93 2 H 5- 2-CHF₂ 94 2 H 5-

95 2 H 5-

96 2 H 5- 2-CH═CCl₂

Besides table 1, the case where X is a sulfur atom:—(table 2)

TABLE 2

Comp. No. Z R R¹ R² R³ R⁴ R⁵ R⁶ n Y  97

H H H — — H H 0 N  98

H H H — — H H 0 N  99

H H H — — H H 0 N 100

H H H H H H H 1 N 101

H H H — — H H 0 N 102

H H H — — H H 0 N 103

H H H H H H H 1 N 104

H H H — — H H 0 N 105

H H H — — H H 0 N mp. 143-145° C. 106

H H H — — H H 0 N 107

H H H H H H H 1 N 108

H H H — — H H 0 N 109

H H H — — H H 0 N 110

H H H H H H H 1 N 111

H H H — — H H 0 N 112

H H H — — H H 0 CH 113

H H H — — H H 0 CH 114

H H H H H H H 1 CH 115

H H H — — H H 0 CH 116

H H H — — H H 0 N 117

H H H — — H H 0 N 118

H H H — — H H 0 N 119

H H H — — H H 0 N 120

H H H H H H H 1 C—CH₃ 121

H H H — — H H 0 C—CH₂F 122

H H H — — H H 0 C—CF₃ 123

H H H — — H H 0 C—CH₂OCH₃ 124

H H H — — H H 0 C—CH₂SC₂H₅ 125

H H H H H H H 1 C—CH₂N(CH₃)₂ 126

H H H H H H H 1 C—CH₂CH═CH₂ 127

H H H — — H H 0 C—(CH₂)₂CN 128

H H H — — H H 0 C—(CH₂)₂COOCH₃ 129

H H H — — H H 0

130

H H H H H H H 1

131

H H H — — H H 0 C—COCH₃ n_(D) ²⁵ 1.6358 132

H H H H H H H 1 C—COCH₂OCH₃ 133

H H H — — H H 0 C—COCCl₃ 134

H H H — — H H 0

135

H H H H H H H 1

136

H H H H H H H 1 C—COOCH₃ 137

H H H H H H H 1 C—COOC₂H₅ 138

H H H — — H H 0 C—COOC₂H₅ 139

H H H — — H H 0

140

H H H — — H H 0 C—S—(CH₂)₃CH₃ 141

H H H — — H H 0

142

H H H — — H H 0

143

H H H — — H H 0

144

H H CH₃ — — H H 0 N 145

H H H — — H H 0

146

H H H H H H H 1 C—COOC{hd 2H₅ n_(D) ²⁴ 1.5978 147

H H H — — H H 0 C—COCH₃ 148

H H H — — H H 0 C—COOCH₃ 149

H H H — — H H 0 C—COOCH₂CF₃ 150

H H H — — H H 0 CH 151

H H H H H H H 1 CH 152

H H H H H H H 1 CH 153

H H H — — H H 0 CH 154

H H H H H H H 1 CH 155

H H H H H H H 1 CH 156

H H H H H H H 1 CH 157

H H H — — H H 0 CH 158

H H H — — H H 0 CH 159

H H H — — H H 0 CH 160

H H H H H H H 1 CH

The case where X is CH—R⁸:—(table 3)

TABLE 3

Comp. No. Z R R¹ R² R³ R⁴ R⁵ R⁶ n R⁸ Y 161

CH₃ H H H — — H 0 H CH 162

H H H H H H H 1 H CH 163

H H H — — H H 0 H CH 164

H H H — — H H 0 H CH 165

H H H — — H H 0 H CH 166

H H H — — H H 0 H CH 167

H H H — — H H 0 H CH 168

H H H — — H H 0 H CH 169

H H H — — H H 0 H N 170

H H H H H H H 1 H N n_(D) ²⁰ 1.5995 171

H H H — — H H 0 H N 172

H H H — — H H 0 H N 173

CH₃ H H — — H H 0 H CH 174

H H H — — H H 0 H CH 175

H H H H H H H 1 H CH 176

H H H — — H H 0 H CH 177

H H H — — H H 0 H CH 178

H H H H H H H 1 H CH 179

H H H — — H H 0 H CH 180

H H H — — H H 0 H N 181

H H H H H H H 1 H N 182

H H H — — H H 0 H N 183

H H H — — H H 0

N 184

H H H — — H H 0 H N 185

H H H H H H H 0 H CH 186

H H H — — H H 0 H CH 187

CH₃ H H — — H H 0

CH 188

H H H — — H H 0 H CH 189

H H H — — H H 0 H N 190

H H H — — H H 0 H N 191

H H H — — H H 0 H N 192

H H H — — H H 0 H N 193

H H H H H H H 1 CH₃ CH 194

H H H — — H H 0 H C—COOC₂H₅ 195

H H H — — H H 0 H

196

H H H — — H H 0 H C—Br 197

H H H H H H H 1 H

198

H H H — — H H 0 CH₃ N

The case where X is an oxygen atom:—(table 4)

TABLE 4

Comp. No. Z R R¹ R² R³ R⁴ R⁵ R⁶ n Y 199

H H H — — H H 0 CH mp. 137-140° C. 200

H H H H H H H 1 CH 201

H H H — — H H 0 CH 202

H H H — — H H 0 CH 203

H H H — — H H 0 CH 204

H H H — — H H 0 N 205

H H H — — H H 0 N 206

H H H — — H H 0 N 207

H H H — — H H 0 N 208

H H H — — H H 0 CH 209

H H H — — H H 0 CH 210

H H H — — H H 0 CH 211

H H H — — H H 0 CH 212

H H H H H H H 1 CH 213

H H H H H H H 1 CH 214

H H H — — H H 0 CH 215

H H H H H H H 1 CH 216

H H H — — H H 0 N 217

H H H — — H H 0 CH 218

H H H — — H H 0 CH 219

H H H — — H H 0 CH 220

H H H — — H H 0 C—CH₃ 221

H H H — — CH₃ H 0 CH 222

H H H — — H H 0

223

H H H — — H H 0

224

H H H — — H H 0 C—CO—(CH₂)₂CH₃

The case where the formula (I) represents the following formula:—(table5)

TABLE 5

Bonding position Com- on the pound pyridine No. m R ring Q_(l) 225 2 H3- — m.p. 90-94° C. (dec.) 226 3 H 3- — 227 2 —CH₃ 3- — 228 2 —C₂H₅ 3- —229 2 —CH(CH₃)₂ 3- 230 2 H 4- — m.p. 154- 157° C. 231 3 H 4- — m.p. 163-165° C. 232 2 H 2- 5-Cl 233 3 H 5- 2-F 234 2 —CH₃ 5- 2-Cl 235 2 H 5-2-Br 236 2 H 5- 2-CH₃ m.p. 157- 160° C. 237 3 H 5- 2-CH₃ m.p. 155.5-158.5° C. 238 2 H 5- 2-C₂H₅ 239 2 H 5- 2-OCH₃ 240 2 H 5- 2-OC₂H₅ 241 2 H5- 2-SCH₃ 242 2 H 5- 2-NO₂ 243 2 H 5- 2-CN 244 2 H 5- 2-NH₂ 245 3 H 5-

246 2 H 5- 2-N(CH₃)₂ 247 2 H 5-

248 2 H 5-

249 2 H 5-

250 2 H 5-

251 2 H 5- 2-CHF₂ 252 2 H 5- 2-CF₃ mp. 134- 146° C. 253 3 H 5- 2-CF₃ 2542 H 5- 2-CCl₃ 255 2 H 5- 2-CF₂Cl 256 2 H 5- 2-CH₂CH₂F 257 2 H 5-2-CH₂CH₂Cl 258 2 H 5- 2-CH₂CF₃ 259 3 H 5- 2-OCHF₂ 260 2 H 5- 2-OCF₃ 2613 H 5- 2-OCH₂CF₃ 262 2 H 5- 2-SCF₃ 263 2 H 5- 2-SCF₂Cl 264 2 H 5- 3-Brm.p. 198- 201° C. 265 2 H 2- 5-CF₃ 266 2 H 5- 2-CH₂C≡CH 267 2 H 5-2-CH₂CH═CH₂ 268 2 H 5- 2-CH═C(Cl)₂ 269 2 H 5- 2,3-Cl₂ 270 2 H 5- 2-Cl,3-CH₃ 271 2 H 5- 2,3,5,6-F₄ 272 2 H 5- 2-CHO 273 2 H 5- 2-CF₂Br

The case where Z is optionally substituted-pyridyl and X is N—R⁷:—(table6)

The formula (I) has the following formula;

In the table 5, “—” for Q_(l) means no substituent and “—” for both R²and R⁵ mean that R² forms a single bond, together with R⁵.

TABLE 6

Comp. Bonding position No. Q_(l) of the pyridine ring R R¹ R² R³ R⁴ R⁵R⁶ n R⁷ Y 274 — 4-position H H CH₃ — — H H 0 H CH mp. 184-187° C. 275 —3-position CH₃ H CH₃ — — H H 0 H CH 276 — 3-position H CH₃ CH₃ — — H H 0H CH mp. 177-180° C. 277 — 4-position H H H CH₃ CH₃ H H 1 H CH mp.190-191° C. 278 — 4-position H H H OH H H H 1 H CH mp. 209-212° C. 2792-F 5-position H H CH₃ — — H H 0 H CH 280 2-Cl 5-position H H H H CH₃ HH 1 H CH 281 2-Cl 5-position H H C₂H₅ — — H H 0 H CH 282 2-Cl 5-positionH H CH₃ — — CH₃ H 0 H CH 283 2-Br 5-position H H CH₃ — — H H 0 H CH 2842-CF₃ 5-position H H CH₃ — — H H 0 H CH 285 2-CH₃ 5-position H H CH₃ — —H H 0 H CH 286 2-CH₃ 5-position H H CH₃ — — H H 0 H CH 287 2-NO₂,5-position H H CH₃ — — H H 0 H CH 3-OCH₃ 288 — 3-position H H H — — H H0 CH₃ CH mp. 107-110° C. 289 2-F 5-position H H H — — H H 0 CH(CH₃)₂ CH290 2-Cl 5-position H H H — — H H 0 CH₃ CH mp. 128-130° C. 291 2-Cl5-position H H H H H H H 1 CH₃ CH 292 2-Cl 5-position H H H — — H H 0 OHCH 293 2-Cl 5-position H H H — — H H 0 OC₂H₅ CH 294 2-Cl 5-position H HH — — H H 0

CH 295 2-Cl 5-position H H H — — H H 0 CH₂OC₂H₅ CH 296 2-Cl 5-position HH H — — H H 0 CH₂CH₂OC₄H₉ CH 297 2-Cl 5-position H H H — — H H 0CH₂CH₂SC₂H₅ CH 298 2-Cl 5-position H H H — — H H 0 CH₂CH═CH₂ CH 299 2-Cl5-position H H H — — H H 0 CH₂CH₂CN CH 300 — 3-position H H H — — H H 0

CH mp. 175-178° C. 301 — 4-position H H H — — H H 0

CH mp. 176-180° C. 302 2-F 5-position H H H H H H H 1

CH 303 2-Cl 5-position H H H — — H H 0

CH mp. 152-153° C. 304 2-Cl 5-position H H H — — H H 0

CH mp. 158-160° C. 305 2-Cl 5-position H H H — — H H 0

CH 306 2-CH₃ 5-position H H H — — H H 0

CH 307 2-Cl 5-position H H H — — H H 0

CH n_(D) ²⁰ 1.6495 308 2-Cl 5-position H H H — — H H 0

CH mp. 154-156° C. 309 2-F 5-position H H H — — H H 0

CH 310 2-Cl 5-position H H H — — H H 0

CH n_(D) ²⁰1.6480 311 2-Br 5-position H H H — — H H 0

CH 312 2-Cl 5-position H H H — — H H 0

CH 313 2-Cl 5-position H H H — — H H 0

CH 314 — 3-position H H H — — H H 0 H C-Cl 315 2-Cl 5-position H H H — —H H 0 H C-F 316 2-Cl 5-position H H CH₃ — — H H 0 H C-Br 317 —4-position H H H H H H H 1 H C-CH₃ 318 2-Cl 5-position H H H — — H H 0 HC-CH₃ 319 2-Cl 5-position H H H — — H H 0 H C-CH₂F 320 2-Cl 5-position HH H — — H H 0 H C-CF₃ 321 — 3-position H H H — — H H 0 H C-CH₂OH 322 2-F5-position H H H H H H H 1 H

323 2-Cl 5-position H H H — — H H 0 H

mp. 135-140° C. 324 2-Cl 5-position H H H — — H H 0 H

mp. 155-158° C. 325 — 3-position H H H H H H H 1 H C-OH 326 2-Cl5-position H H H — — H H 0 H C-OCH₃ 327 2-Cl 5-position H H H — — H H 0H

328 — 4-position H H H — — H H 0 H C-S-C₃H₇ 329 2-CH₃ 5-position H H H —— H H 0 H

330 — 3-position H H H — — H H 0 H

331 2-Cl 5-position H H H — — H H 0 H

332 2-CF₃ 5-position H H H — — H H 0 H

333 2-Cl 5-position H H H — — H H 0 H C-COCH₃ 334 2-F 5-position H H H —— H H 0 H C-COCCl₃ 335 2-NO₂ 5-position H H H — — H H 0 H C-COCH═CH₂ 3362-Cl 5-position H H H — — H H 0 H C-COC₃H₇ mp. 102-105° C. 337 2-Cl5-position H H H — — H H 0 H

mp. 213-215° C. 338 — 3-position H H H H H H H 1 H

339 — 4-position CH₃ H H — — H H 0 H C-COOCH₃ 340 2-Cl 5-position H H H— — H H 0 H C-COOC₂H₅ mp. 169-171° C. 341 2-CN 5-position H H H — — H H0 H C-COOC₄H₉ 342 2-F 5-position H H H — — H H 0 H

343 2-Cl 5-position H H H — — H H 0 H

344 2-Cl 5-position H H H — — H H 0 H C-COS-C₄H₉ 345 2-Cl 5-position H HH — — H H 0 H

mp. 89-94° C. (decomp.) 346 2-CF₃ 5-position H H H — — H H 0 H

347 2,3-Cl₂ 5-position H H H — — H H 0 H

348 2-CHF₂ 5-position H H H — — H H 0 H

349 — 3-position H H H — — H H 0 CH₃ C-COCH₃ 350 2-Cl 5-position H H H —— H H 0 CH₃ C-COC₃H₇ mp. 100-105° C. 351 2-Cl 5-position H H H — — H H 0COCH₃ C-COCH₃ 352 2-CH₃ 5-position H H H — — H H 0 Cl C-Cl 353 —3-position H H H H H H H 1 COOC₂H₅ C-COOC₂H₅ 354 2-Cl 5-position H H H —— H H 0

glass 355 2-CF₃ 5-position H H H — — H H 0

356 — 4-position H H H — — H H 0

357 2-Cl 5-position H H H — — H H 0

358 — 3-position H H H CH₃ H H H 1 H N 359 2-Cl 5-position H H CH₃ — — HH 0 H N 360 2-Cl 5-position H CH₃ CH₃ — — H H 0 H N 361 2-Cl 5-positionH H H — — H H 0 CH₃ N 362 2-SCN 5-position H H H — — H H 0 CH(CH₃)₂ N363 2-F 5-position H H H — — H H 0 CH₂CH₂Cl N 364 2-Cl 5-position H H H— — H H 0 CH₂CH═CH₂ N n_(D) ³⁰1.5854 365 2-Cl 5-position H H H — — H H 0CH₂CCl═CCl₂ N 366 2-Cl 5-position H H H — — H H 0 CH₂CH₂CN N 367 2-F5-position H H H — — H H 0 CH₂C═CH N 368 2-CF₃ 5-position H H H — — H H0 CH₂CH₂N(C₂H₅)₂ N 369 2-Cl 5-position H H H H H H H 1 CH₂OCH₃ N 370 —3-position H H H — — H H 0 CH₂CH₂SC₂H₅ N 371 2-CH₂F 5-position H H H — —H H 0 CH₂SC₄H₉ N 372 2-Cl 5-position H H H — — H H 0 CH₂CN N 373 2-Cl5-position H H H — — H H 0 CH₂Si(CH₃)₃ N 374 5-CF₃ 2-position H H H — —H H 0 CH₂Si(CH₃)₃ N 375 2-Cl 5-position H H H H H H H 1

N 376 2-NO₂ 5-position H H H — — H H 0

N 377 — 3-position H H H — — H H 0

N 378 2-Cl 5-position H H H — — H H 0

N 379 5-OCF₃ 2-position H H H — — H H 0

N 380 2-Cl 5-position H H H — — H H 0

N mp. 126-128° C. 381 2-Cl 5-position H H H — — H H 0

N mp. 146-148° C. 383 2-Cl 5-position H H H — — H H 0

N mp. 128-131° C. 383 — 3-position H H H — — H H 0

N 384 2-CH₃ 5-position H H H H H H H 1

N 385 2-Cl 5-position H H H H H H H 1

N 386 2-Cl 5-position H H H H H H H 1

N 387 2-F 5-position H H H — — H H 0

N 388 2-Cl 5-position H H H — — H H 0

N 389 2-Cl 5-position H H H — — H H 0

N 390 2-CH₃ 5-position H H H — — H H 0

N 391 2-F 5-position H H H — — H H 0 CH₂COCH₃ N 392 2-Cl 5-position H HH — — H H 0

N 393 2-Cl 5-position H H H — — H H 0

N 394 — 3-position CH₃ H H — — H H 0 COCH₃ N 395 2-Cl 5-position H H H —— H H 0 CHO N 396 2-Cl 5-position H H H — — H H 0 COCH₃ N mp. 144.5-146°C. 397 2-Cl 5-position H H H H H H H 1 COCH₃ N 398 2-F 5-position H H H— — H H 0 COCCl₃ N 399 2-Cl, 5-position H H H — — H H 0 COC₃H₇ N 4-F 4002-C₂H₅ 5-position H H H — — H H 0 COCH₃ N 401 2-Cl 5-position H H H — —H H 0 COC(CH₃)₃ N 402 2-CH₃ 5-position H H H — — H H 0

N 403 2,3-F₂ 5-position H H H — — H H 0 COCH₂OCH₃ N 404 2-Br 5-positionH H H — — H H 0 COCH═CH₂ N 405 2-Cl 5-position H H H — — H H 0

N 406 — 3-position H H H — — H H 0

N 407 — 4-position H H H H H H H 1

N 408 2-Cl 5-position H H H — — H H 0

N mp. 146-150° C. 409 2-F 5-position H H H — — H H 0

N mp. 149-152° C. 410 2-Cl 5-position H H H — — H H 0

N 411 2-Cl 5-position H H H — — H H 0

N 412 — 3-position H H H — — H H 0

N 413 2-CH═CCl₂ 5-position H H H — — H H 0

N 414 2-CF₃ 5-position H H H — — H H 0

N 415 2-CH₃ 5-position H H H — — H H 0

N 416 2-Cl 5-position H H H — — H H 0

N 417 2-Cl 5-position H H H — — H H 0

N 418 2-Cl 5-position H H H — — H H 0

N 419 — 3-position H H H H H H H 1

N 420 2-F 5-position H H H — — H H 0

N 421 2-CH₃ 5-position H H H — — H H 0

N 422 2-Cl 5-position H H H — — H H 0

N 423 2,6-Cl₂ 4-position H H H — — H H 0

N 424 2-Cl 5-position H H H — — H H 0

N mp. 118-122° C. 425 2-Cl 5-position H H H — — H H 0

N 426 — 3-position H H H H CH₃ H H 1 COOCH₃ N 427 2-F 5-position H H H —— H H 0 COOC₂H₅ N 428 2-Cl 5-position H H H — — H H 0 COOC₂H₅ N mp.125-126° C. 429 2-CH₃ 5-position H H H — — H H 0 COOC₄H₉ N 430 2-Cl5-position H H H — — H H 0 COOCH₂CF₃ N 431 2-Cl 5-position H H H — — H H0

N mp. 135-140° C. 432 2-Cl 5-position CH₃ H H — — H H 0

N 433 2-Cl 5-position H H H — — H H 0

N 434 2-CHF₂ 5-position H H H — — H H 0

N 435 2-Cl 5-position H H H — — H H 0 COSC₂H₅ N 436 2-Cl 5-position H HH — — H H 0

N 437 2,3-F₂ 5-position H H H — — H H 0

N 438 2-Cl 5-position H H H — — H H 0

N mp. 191-192° C. 439 2-Cl 5-position H H H — — H H 0

N 440 2-Cl 5-position H H H — — H H 0

N 441 2-COOCH₃ 6-position H H H — — H H 0

N 442 2-Cl 5-position H H H — — H H 0

N 443 2-Cl 5-position H H H — — H H 0

N 444 2-Cl 5-position H H H — — H H 0 CON(CH₃)₂ N mp. 186-188° C. 4452-Cl 5-position H H H — — H H 0

N mp. 120-123° C. 446 2-F 5-position H H H — — H H 0

N 447 2-Cl, 6-F 5-position H H H — — H H 0

N 448 2-CN 5-position H H H — — H H 0

N 449 — 4-position H H H H H H H 1

N 450 2-Cl 5-position H H H — — H H 0

N 451 2-Cl 5-position H H H — — H H 0

N 452 — 3-position H H H — — H H 0

N n_(D) ²⁴1.5760 453 2-Cl 5-position H H H — — H H 0

N n_(D) ²⁰1.5615 454 2-Cl 5-position H H H — — H H 0

N 455 2-Cl 5-position H H H — — H H 0

N 456 2-Cl 5-position H H — H H — H 1 H CH

In addition to table 5, there follow: the case (table 7) where theformula (I) represents the following formula;

the case (table 8) where the formula (I) represents the followingformula;

the case (table 9) where the formula (I) represents the followingformula;

the case (table 10) where the formula (I) represents the followingformula;

TABLE 7

Compound Bonding potition No. Het of the heterocycle Q_(l) R m 457 O 2 —H 2 458 O 2 — H 3 mp. 194˜196° C. 459 O 3 — H 3 460 S 2 — H 2 461 S 2 —H 3 mp. 189˜190° C. 462 S 3 — H 3 mp. 196˜198° C. 463 S 3 — —CH₃ 2 464 N2 1-H H 2 mp. 201˜205° C. 465 N 2 1-H H 3 mp. 183˜185° C. 466 N 3 1-H H3 467 N 2 1-CH₃ H 2 468 N 2 1-CH₃ H 3 mp. 207˜213° C. 469 N 2 1-C₂H₅ H 2470 N 3 1-CH₃ H 3 471 O 2 5-CH₃ H 2 mp. 151˜152° C. 472 O 2 5-CH₃ H 3473 O 3 5-CH₃ H 2 474 S 2 5-CH₃ H 2 475 S 3 5-CH₃ H 3 476 N 3 1-H, 5-CH₃H 3 477 N 3 1-H, 5-CH₃ H 2 478 O 3 2,5-(CH₃)₂ H 3 479 S 3 2,5-(CH₃)₂ H 3480 O 3 5-F H 2 481 O 2 4-Cl H 2 482 O 2 5-Cl H 2 mp. 130˜131° C. 483 O3 5-Cl H 3 484 S 3 5-Cl H 2 485 N 3 1-CH₃, 5-Cl H 3 486 O 3 5-Br H 2 487S 2 5-Br H 3 mp. 184˜186° C. 488 O 2 4,5-Cl₂ H 2 489 S 3 4,5-Cl₂ H 2 490S 2 4,5-Br₂ H 2 491 O 2 5-NO₂ H 2 492 S 2 4-NO₂ H 3 493 S 2 5-NO₂ H 2494 N 3 1-CH₃, 5-NO₂ H 3 495 O 2 5-CN H 2 mp. 212˜215° C. 496 O 3 5-CN H3 497 S 3 5-CN H 2 498 N 3 1-CH₃, 5-CN H 2 499 O 2 5-CF₃ H 2 500 O 25-CHF₂ H 3 501 S 3 4-CF₂ H 3 502 N 3 1-CH₃, 5-CF₃ H 2 503 S 2 5-OCH₃ H 2504 O 2 5-SCH₃ H 3 505 S 3 2,5-(SCH₃)₂ H 2 506 O 2 5-SCF₃ H 2 mp.143˜144° C. 507 O 2 5-SCF₃ H 3 mp. 120˜124° C. 508 S 2 5-CH═CCl₂ H 2 509O 2

H 2 mp. 127˜129° C. 510 O 2 5-COOC₂H₅ H 2 511 S 2 5-CHO H 2 512 S 24-CH₃ —CH₃ 2 mp. 170˜171.5° C.

TABLE 8

Compound Bonding position No. Het of the heterocycle Q_(l) R m 513 O 3 —H 3 514 O 4 — H 2 515 O 4 — H 3 516 O 4 — —CH₃ 2 517 O 5 — H 3 518 O 35-CH₃ H 3 mp. 186˜188° C. 519 O 5 3-CH₃ H 3 mp. 200˜201° C. 520 O 53-C₂H₅ H 2 521 O 5 3-C₂H₇-iso H 2 522 O 5 3-F H 3 523 O 5 3-Cl H 2 524 O5 3-Br H 2 525 O 5 3-OH H 2 526 O 5 3-NO₂ H 3 527 O 5 3-CN H 3 528 O 53-CF₃ H 2 529 O 5 3-CF₃ H 3 mp. 177˜180° C. 530 O 5 3-CHF₂ H 2 531 O 53-CF₂Cl H 2 532 O 5 3-CH₂Cl H 2 533 O 5 3-CH₂OCH₃ H 2 534 O 53-CH₂OCH(CH₃)₂ H 2 535 O 5 3-CCl₃ H 2 536 O 5 3-OCH₃ H 3 537 O 5 3-OCF₃H 2 538 O 4 2,5-(CH₃)₂ H 2 539 S 3 — H 3 540 S 4 — H 2 541 S 5 — H 2 542S 3 5-CH₃ H 3 543 S 5 3-CH₃ H 2 544 S 5 3-F H 2 545 S 3 5-Cl H 2 546 S 53-Cl H 2 547 S 3 5-Br H 2 548 S 5 3-NO₂ H 3 549 S 5 3-SCF₃ H 2 550 N 51-H H 2 mp. 190˜193° C. 551 N 5 1-H H 3 552 N 4 1-H H 2 mp. 196˜198° C.553 N 4 1-H —CH₃ 2 554 N 4 1-H H 3 mp. 222˜225° C. 555 N 3 1-CH₃ H 2 mp.212˜215° C. 556 N 4 1-CH₃ H 2 mp. 179˜180° C. 557 N 4 1-CH₃ —CH₃ 3 558 N5 1-CH₃ H 2 559 N 4 1-C₂H₅ H 2 560 N 4 1-C₂H₅ H 3 mp. 145˜148° C. 561 N4 1-C₃H₇ H 3 mp. 99˜101° C. 562 N 4 1-C₃H₇-iso H 2 563 N 4 1-C₃H₇-iso H3 mp. 136˜137° C. 564 N 4 1-CH₂CH═CH₂ H 3 mp. 109˜112° C. 565 N 41-CH₂C≡CH H 2 566 N 4 1-C₄H₉-tert H 2 mp. 126˜128° C. 567 N 41-C₄H₉-tert H 3 mp. 153˜156° C. 568 N 4

H 2 mp. 151˜153° C. 569 N 4

H 3 mp. 177˜180° C. 570 N 4

H 2 mp. 111˜113° C. 571 N 4

H 3 mp. 159˜163° C. 572 N 4 1-CF₃ H 2 573 N 3 1-CH₂CF₃ H 2 574 N 41-CH₂CF₃ H 2 575 N 5 1-H, 3-CH₃ H 2 mp. 183˜185° C. 576 N 5 1-H, 3-CH₃ H3 577 N 3 1-H, 5-Cl H 2 578 N 3 1-CH₃, 5-F H 2 579 N 3 1-CH₃, 5-Cl H 2mp. 195˜198° C. 580 N 3 1-CH₃, 5-Cl H 3 mp. 222˜224° C. 581 N 3 1-C₂H₅,5-Cl H 2 582 N 3 1-C₃H₇-iso, 5-Cl H 2 583 N 5 1-CH₃, 5-Cl H 2 584 N 31-H, 5-CF₃ H 2 585 N 3 1-CH₃, 5-CF₃ H 2 586 N 5 1-CH₃, 5-CF₃ H 2 587 N 41,3,5-(CH₃)₃ H 3 mp. 192˜194° C. 588 N 5 1-CH₂CF₃ H 2 mp. 165˜168° C.

TABLE 9

Compound Bonding position No. Het of the heterocycle Q_(l) R m 589 O 4 —H 2 590 O 5 — H 2 591 O 5 — H 3 592 O 4 2-CH₃ H 2 593 O 5 2-CH₃ H 2 594O 5 2-CH₃ H 3 595 O 5 4-CH₃ H 2 mp. 200˜202° C. 596 O 5 4-CH₃ H 3 mp.221˜224° C. 597 O 5 2-F H 2 598 O 5 2-Cl H 2 599 O 5 2-Cl H 3 600 O 52-CF₃ H 2 601 O 5 2-SCF₃ H 2 602 O 5 2-OCF₃ H 2 603 O 5 2,4-(CH₃)₂ H 2604 O 2 5-COOC₂H₅ H 3 605 S 4 — H 2 mp. 213˜216° C. 606 S 4 — H 3 mp.181˜183° C. 607 S 5 — H 2 mp. 169˜174° C. 608 S 5 — —CH₃ 2 609 S 5 ——C₃H₇-iso 2 610 S 5 — H 3 611 S 4 2-CH₃ H 2 mp. 170˜172° C. 612 S 42-CH₃ H 3 mp. 203˜208° C. 613 S 5 2-CH₃ H 2 mp. 162˜166° C. 614 S 52-CH₃ —CH₃ 2 615 S 5 2-CH₃ —CH₃ 3 616 S 5 2-C₂H₅ H 2 617 S 5 2-CH₃H₇-isoH 3 618 S 5 4-CH₃ H 2 619 S 4 2-F H 2 620 S 4 2-Cl H 2 mp. 162˜165° C.621 S 4 2-Cl H 3 mp. 190˜194° C. 622 S 5 2-F H 3 623 S 5 2-Cl H 2 mp.191˜192° C. 624 S 5 2-Cl H 3 mp. 203˜205° C. 625 S 5 2-Cl —CH₃ 3 626 S 52-Cl —C₂H₅ 3 627 S 5 2,4-Cl₂ H 2 mp. 179˜181° C. 628 S 4 2-NO₂ H 2 629 S5 2-NO₂ H 3 630 S 4 2-CN H 2 631 S 5 2-CN H 2 632 S 4 2-SCH₃ H 3 633 S 52-SH H 2 634 S 5 2-SCH₃ H 3 635 S 5 2-SCHF₂ H 2 636 S 5 2-SCF₃ H 2 637 S5 2-SCF₂Cl H 2 638 S 5 2-SCH₂CF₃ H 2 639 S 5

H 2 640 S 5 2-SCN H 2 641 S 4 2-NH₂ H 2 mp. 165˜167° C. 642 S 4

H 2 643 S 4 2-OCH₃ H 3 644 S 5 2-OCH₃ H 3 645 S 5 2-OCF₂ H 2 646 S 52-OCHF₂ H 3 647 S 5 2-CH₂Cl H 2 648 S 5 2-CHF₂ H 2 649 S 5 2-CF₃ H 2 650S 5 2-CF₃ H 3 651 S 5 2-CF₂CHF₂ H 2 652 S 5

H 3 653 S 4

H 2 mp. 169˜172° C. 654 S 4

H 3 mp. 158˜159° C. 655 N 2 1-H H 2 mp. 239˜240° C. 656 N 4 1-H H 2 657N 4 1-H H 3 mp. 169˜173° C. 658 N 2 1-CH₃ H 2 mp. 248˜252° C. 659 N 51-CH₃ H 2 660 N 2

H 2 mp. 142˜145° C. 661 N 5 1-H, 4-CH₃ H 2 662 N 4 1-H, 2-F H 3 663 N 41-H, 2-Cl H 2 664 N 2 1-H, 4-NO₂ H 2 665 N 4 1-H, 2-SCF₃ H 2 666 N 41,2-(CH₃)₂ H 2 667 N 4 1-CH₃, 2-CF₃ H 2 668 O 2 5-COOH H 3 669 S 52-NHCH₃ H 2 670 S 5 2-N(CH₃)₂ H 3 mp. 188˜191° C. 671 S 5

H 2 672 S 5 2-CH₃ H 4 673 S 2 5-CONH₂ H 2 674 S 2 5-CONHCH₃ H 2 675 S 25-CON(CH₃)₂ H 3 676 S 5 2-SOCH₃ H 2 677 S 5 2-SO₂CH₃ H 2 678 S 52-N(CH₃)₂ H 2 mp. 149˜150° C. 679 S 5 2-SCH₃ H 2 mp. 150˜153° C. 680 S 52-Br H 3

TABLE 10

Compound No. Z R m 681

H 2 mp. 206˜210° C. 682

H 3 683

H 2 mp. 265˜267° C. 684

H 2 685

H 3 686

—CH₃ 2 687

H 2 688

H 2 689

H 2 690

H 3 691

H 2 692

H 2 mp. 221˜225° C. 693

H 2 694

H 2 mp. 178˜180° C. 695

H 3 696

H 2 697

H 2 698

H 2 699

H 2 700

H 2 701

H 3 702

—CH₃ 2 703

H 2 704

—CH₃ 3 705

H 2 mp. 188˜190° C. 706

H 3 mp. 207˜210° C. 707

H 2 708

H 2 709

H 2 710

H 3 711

H 2 712

H 2 713

H 2 714

H 2 715

H 2 716

H 2 717

H 2 718

H 2 mp. 163˜166° C. 719

H 2 720

H 3 721

—CH₃ 3 722

H 2 723

—CH₃ 2 724

H 2 725

H 3 726

H 3 mp. 144˜148° C. 727

H 2 728

H 3 729

H 2 730

H 3 731

H 2 732

H 2 733

H 2 734

H 2 mp. 142˜143° C. 735

H 2 736

H 3 737

H 2 738

H 2 739

H 2 740

H 3 741

H 2 742

H 2 743

H 2 744

H 2 mp. 212˜215° C. 745

H 3 746

H 2 747

H 2 748

H 3 749

H 2 750

H 2 751

H 2 752

H 2 753

H 2 754

H 2 755

H 2 m.p. 185-187° C. 756

H 2 m.p. 216-217° C. 757

H 3 758

H 2 m.p. 188-189° C. 759

H 2 m.p. 200-203° C. 760

H 3 m.p. 219-222° C. 761

H 2 762

H 2 m.p. 259-260° C. 763

—CH₃ 2 m.p. 173-174° C. 764

H 2 m.p. 216-218° C. 765

H 2 766

H 2 767

H 3 768

H 2 769

H 3 770

H 2 771

H 3 772

H 2 773

H 2 774

H 2 775

H 2 776

H 2 777

H 3 778

H 2 779

H 2 780

H 2 781

H 2 782

H 2 783

H 2 784

H 3 785

H 2 786

H 2 787

H 2 788

H 3 789

H 2 790

H 2 m.p. 172-175° C. 791

H 3 792

H 2 793

H 2 794

H 2 795

H 2 796

H 2 797

H 2 798

H 2

Besides table Nos. 5 to 10, there follows the case where X is N—R⁷:—(table 11)

TABLE 11

Comp. No. Z R R¹ R² R³ R⁴ R⁵ R⁶ n R⁷ Y 799

H H H — — H H 0 H N 800

CH₃ H H — — H H 0 H N 801

H H H H H H H 1 H N 802

H H H H H H H 1 H N 803

H H H H H H H 1 H N 804

H H H H H H H 1 H N 805

H H H — — H H 0 H N mp. 149-150° C. 806

H H H — — H H 0 H N 807

H H H — — H H 0 H N 808

H H H H H H H 1 H N 809

H H H — — H H 0 H N 810

H H H — — H H 0 H N 811

H H H H H H H 1 H N 812

H H H — — H H 0 H N 813

H H H H H H H 1 H N mp. 123-128° C. 814

H H H H H H H 1 H N 815

H H H H H H H 1 H N 816

H H H H H H H 1 H N 817

H H H H H H H 1 H N 818

H H H — — H H 0 H N mp. 141-145° C. 819

H H H H H H H 1 H N 820

H H H H H H H 1 H N 821

H H H H H H H 1 H N 822

H H H H H H H 1 H N 823

H H H — — H H 0 H N 824

CH₃ H H — — H H 0 H N 825

H H H — — H H 0 H N 826

H H H — — H H 0 H N 827

H H H — — H H 0 H N mp. 181-183° C. 828

H H H H H H H 1 H N 829

H H H — — H H 0 H N 830

H H H — — H H 0 H N 831

H H H — — H H 0 H N mp. 142-144° C. 832

H H H — — H H 0 H N 833

H H H — — H H 0 H N mp. 216-219° C. 834

H H H — — H H 0 H N 835

H H H CH₃ CH₃ H H 1 H CH mp. 210-213° C. 836

H H H H H H H 1 CH₃ CH 837

H H H H H H H 1 C₂H₅ CH 838

H H H — — H H 0

CH 839

H H H — — H H 0

CH 840

H H H — — H H 0

CH 841

H H H — — H H 0

CH mp. 154-156° C. 842

H H H H H H H 1

CH glass 843

H H H — — H H 0

CH n_(D) ²⁰1.5980 844

H H H H H H H 1

CH 845

H H H H H H H 1

CH 846

H H H — — H H 0

CH 847

H H H — — H H 0

CH 848

H H H — — H H 0 H C—COOC₂H₅ mp. 153-155° C. 849

H H H H H H H 1 H

850

H H H H H H H 1 H

851

H H H H H H H 1 H C—CO(CH₂)₃CH₃ 852

H H H — — H H 0 H

853

H H H — — H H 0 CH₃ N 854

H H H — — H H 0 C(CH₃)₃ N 855

H H H H H H H 1 CH₂SCH₃ N 856

H H H H H H H 1 CH₂CH₂OC₂H₅ N 857

H H H — — H H 0 CH₂COCH₃ N 858

H H H — — H H 0 COCH₃ N 859

H H H H H H H 1 CHO N 860

H H H H H H H 1 COCH₃ N 861

H H H — — H H 0 CON(C₂H₅)₂ N 862

H H H — — H H 0

N 863

H H H — — H H 0 COCH₃ N mp. 134-136° C. 864

H H H — — H H 0

N 865

H H H — — H H 0

N 866

H H H — — H H 0

N 867

H H H — — H H 0 COOC₂H₅ N 868

H H H H H H H 1

N 869

H H H — — H H 0

N 870

H H H — — H H 0

N mp. 156-158° C. 871

H H H H H H h 1

N 872

H CH₃ H — — H H 0 H CH 873

H H H — — H H 0 H

874

H H H — — H H 0 H

875

H H H — — H H 0 CH₃ N 876

H H H — — H H 0 COCH₂OCH₃ N 877

H H H — — H H 0

N 878

H H H — — H H 0

N 879

H H H — — H H 0

N 880

H H H — — H H 0

N 881

H H H — — H H 0

N

The case where the formula (I) represents the following formula: —(table12)

TABLE 12

Comp. No. Z R R¹ R² R³ R⁴ R⁵ R⁶ n L Hal 882

H H H — — H H 0 Cl Cl 883

H H H — — H H 0 Cl Cl 884

H H H — — H H 0 Br Br mp. 140-143° C. (decomp.) 885

H H H — — H H 0 Cl Br

The case where the formula (I) represents the following formula: —(table13)

TABLE 13 Comp. No. Compounds 886

mp 170-175° C. (decomp.) 887

Typical examples of synthesizing the intermediate compound of theformula (II) are shown below.

EXAMPLE 36

Trimethylenediamine (37 g) was dissolved in 120 ml of acetonitrile, anda solution of 14.8 g of 5-chloromethyl-2-methylthiazole in 30 ml ofacetonitrile was added dropwise at 10 to 15° C. After the addition, themixture was stirred at 30 to 40° C. for a while, and then 8 g of a 50%aqueous solution of sodium hydroxide was added. Subsequently, thevolatile materials were removed at a bath temperature of less than 50°C. under 5 mmHg. The inorganic materials were removed from the residueby filtration to give 16.7 g ofN-(2-methyl-5-thiazolylmethyl)trimethylenediamine (purity about 90%) asa colorless oil.

n_(D) ²²: 1.5126

EXAMPLE 37

Ethylenediamine (30 g) was dissolved in 120 g of acetonitrile, and asolution of 17.6 g of 5-bromomethyl-3-methylisoxazole in 30 ml ofacetonitrile was added dropwise at 5 to 10° C. After the addition, themixture was stirred for 1 hour with a care taken not to permit thetemperature of the reaction system to rise above 20° C. Then, most ofthe volatile materials were removed under vacuum (less than 2 mmHg)while maintaining the bath temperature at 20° C. Ice water was added tothe residue, and the mixture was extracted with dichloromethane. Thedichloromethane layer was dehydrated, and dichloromethane was distilledoff under reduced pressure to give 10.0 g ofN-(3-methyl-5-isoxazolylmethyl)ethylenediamine (purity about 95%) as acolorless oil.

NMR spectrum (δ in CDCl₃):

NH, NH₂: 1.47 (ppm)

—CH₂CH₂—: 2.23

—CH₃: 2.7

—CH₂—: 5.8

Hetero-H: 5.9

EXAMPLE 38

At room temperature 11 g of 1-methyl-4-pyrazole carbaldehyde was slowlyadded to 37 g of ethylenediamine in 150 ml of dry acetonitrile.Molecular sieves 4A (a product of Wako Pure Chemicals, Co.) were addedas a dehydrating agent to the solution. The mixture was stirred at roomtemperature for 2 hours, and filtered. Acetonitrile was distilled offunder reduced pressure from the filtrate. To the residue was added 100ml of ethanol, and then 4 g of sodium borohydride was added little bylittle at room temperature. The mixture was then stirred at roomtemperature for 2 hours, and ethanol was distilled off under reducedpressure. Water was added to the residue, and the mixture was extractedwith dichloromethane. The solvent was distilled off from thedichloromethane layer, and the residue was vacuum-distilled to give 10 gof N-(1-methyl-4-pyrazolylmethyl)trimethylenediamine as a colorless oil.

bp.: 120-125° C./0.8 mmHg

EXAMPLE 39

A solution composed of 12.6 g of 3-acetylthiophene, 30 g ofethylenediamine and 150 ml of benzene was refluxed with stirring whileremoving water as an azeotrope. When formation of water was no longerobserved, benzene was distilled off under reduced pressure. Ethanol (100ml) was added to the residue, and subsequently, 4 g of sodiumborohydride was added little by little. The mixture was then stirred at40° C. for 2 hours. Ethanol was distilled off under reduced pressure. Asmall amount of the inorganic matter was removed from the residue.Subsequent vacuum distillation have 8.2 g ofN-[1-(3-thienyl)ethyl]ethylenediamine.

bp.: 102-105° C./3.5 mmHg

Novel compounds of the formula (II) obtained by the same methods asdescribed in Examples 36 to 39 are shown below.

TABLE 14

Z R m

H 3

H 2 n_(D) ²⁰ 1.5523

H 3 n_(D) ²⁰ 1.5495

H 3

H 2 bp 108˜110° C./ 4 mmHg

H 3 bp 135˜140° C./ 0.5 mmHg

H 2

H 2 n_(D) ²⁰ 1.4775

H 3 n_(D) ²³ 1.4752

H 3

H 3

H 3

H 3

H 3 n_(D) ²⁰ 1.4683

H 2

H 3

H 2 n_(D) ²⁰ 1.5335

H 3 n_(D) ²⁰ 1.5230

H 2

H 3

H 2 bp 125˜127° C./ 1 mmHg

—CH₃ 2 bp 133˜135° C./ 1.2 mmHg

H 3 n_(D) ²⁰ 1.5251

H 3

H 3 n_(D) ²⁰ 1.5085

H 2 n_(D) ²⁰ 1.5045

H 2 n_(D) ²⁰ 1.4651

H 2

H 2 n_(D) ²⁰ 1.4940

H 3 n_(D) ²⁰ 1.4904

H 3

H 2 n_(D) ²³ 1.5003

H 3

H 2 n_(D) ²⁷ 1.5160

H 3 n_(D) ²⁷ 1.5130

H 2 n_(D) ²⁰ 1.5722

H 2

H 3

H 2 n_(D) ²⁴ 1.5205

H 2 n_(D) ²⁴ 1.5691

H 3

H 2

H 2

H 2 n_(D) ²⁰ 1.5788

H 3

H 2

H 2

H 2

H 2 n_(D) ²⁰ 1.5457

H 2

H 3

H 2

H 3 bp 90° C./ 2.5 mmHg

H 2 n_(D) ¹⁷ 1.4715

H 2

H 2

EXAMPLE 40

A solution composed of 6-chloronicotinaldehyde (14.2 g),2-aminoethanethiol (7.7 g) and benzene (80 ml) was heated with stirringfor 5 hours while removing water as an azeotrope. After the reaction,benzene was distilled off under reduced pressure, and further volatilematerials were removed at 1 mmHg and 70° C. to give2-(2-chloro-5-pyridyl)thiazolidine (18 g) as a residue. Ten grams of2-(2-chloro-5-pyridyl)thiazolidine was dissolved in 100 ml of ethanol,and sodium borohydride was added. With stirring, the mixture wasgradually heated and thereafter refluxed for 1 hour. Ethanol wasdistilled off under reduced pressure, and chloroform was added to theresidue. Insoluble materials were separated by filtration and thechloroform layer was washed with water and dehydrated. Chloroform wasdistilled off under reduced pressure to give the desiredN-(2-chloro-5-pyridylmethyl)2-aminoethanethiol (8.3 g).

n_(D) ²⁴: 1.5917.

EXAMPLE 41

A solution composed of 6-methylnicotinaldehyde (12.1 g,3-aminopropanethiol (9.1 g) and benzene (120 ml) was refluxed for 5hours with stirring while removing water as an azeotrope. After thereaction, benzene was distilled off under reduced pressure, and volatilematerials were removed at 1 mmHg and 70° C. As a residue,3-pyridyltetrahydrothiazine (16.5 g) was obtained. Then,3-pyridyltetrahydrothiazine (10 g) was dissolved in 100 ml of ethanol,and sodium borohydride was added. The mixture was gradually heated withstirring, and subsequently refluxed for 1 hour. Ethanol was distilledoff under reduced pressure. Chloroform was added to the residue, andinsoluble materials were separated by filtration. The chloroform layerwas washed with water and dehydrated. On distilling off chloroform underreduced pressure, the desired N-(3-pyridyl)3-aminopropanethiol (6.2 g)was obtained.

n_(D) ²⁰: 1.5733

Compund No. II of the following formula was also prepared by the samemethod as in Examples 40 and 41.

N-(2-chloro-5-pyridylmethyl)3-aminopropanethiol

(n_(D) ²²: 1.5890)

EXAMPLE 42

Ethylenediamine (60 g) was dissolved in benzene (200 ml), and5-formylpyrimidine (21.6 g) was added at room temperature. Subsequently,the mixture was heated, and refluxed for 3 hours while removing water asan azeotrope. After the reaction, benzene and the excess ofethylenediamine were distilled off under reduced pressure. The residuewas dissolved in ethanol (200 ml). Sodium borohydride. (8.4 g) was addedportionwise to this solution at room temperature, and subsequently themixture was stirred at room temperature for 5 hours. Ethanol wasdistilled off under reduced pressure. Dichloromethane (100 ml) was addedto the residue, and a dichloromethane-soluble portion was separated.Dichloromethane was distilled off from the dichloromethane layer underreduced pressure to give N-(5-pyrimidinylmethyl)-ethylenediamine (25.8g) as a colorless oil. n_(D) ²⁵=1.5532.

EXAMPLE 43

Ethylenediamine (30 g) was dissolved in acetonitrile (200 ml), andpyrazinylmethyl chloride (12.9 g) was added dropwise to this solution at5 to 10° C. After addition, the mixture was stirred at room temperaturefor 1 hour. Then, a 50% aqueous solution of sodium hydroxide (8 g) wasadded, and thereafter, volatile materials were removed at a bathtemperature of 60° C. under 5 mmHg. The inorganic salt was then removedby filtration. Thus, N-(pyrazinylmethyl)ethylenediamine (14.1 g) wasobtained as a colorless oil. n_(D) ²⁰=1.5359.

EXAMPLE 44

A solution of 2-cyano-5-pyridylmethyl chloride (4.6 g) in acetonitrile(20 ml) was added dropwise to a solution of ethylenediamine (9 g) inacetonitrile (50 ml) at 5 to 10° C. After the addition, the mixture wasstirred at room temperature for 3 hours. Acetonitrile and the excess ofethylenediamine were distilled off under reduced pressure from thereaction mixture. Dichloromethane was added to the residue, and aportion of it soluble in dichloromethane was separated. Dichloromethanewas distilled off under reduced pressure. Volatile materials wereremoved at 50° C. and 1 mmHg to giveN-(2-cyano-5-pyridylmethyl)ethylenediamine (4.5 g) as a colorless oil.

n_(D) ²⁰=1.5718

EXAMPLE 45

5-Trifluoromethylpicoline aldehyde (3.5 g) was added dropwise at roomtemperature to a solution of trimethylenediamine (7.4 g) in benzene (70ml). After the addition, the mixture was gradually heated with stirring,and then while separating water as an azeotrope, refluxed for 2 hours.Benzene was distilled off under reduced pressure, and then the residuewas dissolved in ethanol (100 ml). With stirring at 10 to 15° C., sodiumborohydride (0.9 g) was added little by little. The mixture was thenstirred at room temperature for 2 hours. Ethanol was distilled off atless than 30° C. Dichloromethane was added to the residue, and a portionof it soluble in dichloromethane was separated. Dichloromethane wasdistilled off under reduced pressure, and volatile materials wereremoved at 1 mmHg and less than 60° C. to giveN-(5-trifluoromethyl-2-pyridylmethyl)trimethylenediamine (3.5 g) as acolorless oil.

n_(D) ²⁰1.4651

EXAMPLE 46

A solution of 8.1 g of 2-chloro-5-chloromethylpyridine in 30 ml ofacetonitrile was added dropwise to a mixture of 14.8 g of1,2-diaminopropane, 5 g of 40% sodium hydroxide solution, and 100 ml ofacetonitrile at 0° C. during 2 hours with vigorous stirring. Afterstirring for a short time at room temperature, the acetonitrile, waterand excess 1,2-diaminopropane were removed under reduced pressure.Inorganic salt was filtered off with suction from the residue. Thefiltrate was the desired product,2-amino-1-(2-chloro-5-pyridylmethylamino)propane (9.3 g).

n_(D) ¹⁷1.5450

In the same way as in Example 46, the following compounds were produced.

N-methyl-N′-3-pyridylmethylethylenediamine

bp. 140° C./2.5 mmHg

2-amino-2-methyl-1-(3-pyridylmethylamino)propane

bp. 115° C./1.5 mmHg

2-aminomethyl-2-methyl-1-(1-methyl-4-pyrazolylmethyl)propane

n_(D) ²⁵1.5109

EXAMPLE 47

A solution of 18.6 g of N-(2-chloro-5-pyridylmethyl) ethylenediamine, 11g of 1-methylpyrazole-4-carbaldehyde in 150 ml of benzene was stirred onwarm water bath. After a short time, water was separated from thesolution and the Schiff base was obtained. The benzene and water werethen removed under reduced pressure and 100 ml of ethanol was added tothe residue. To the solution 3.8 g of sodium-borohydride was addedportionwise at room temperature and the mixture was stirred for 1 day.After removing the ethanol under reduced pressure, the residue wasdissolved in dichloromethane and washed with water. The treatment ofdichloromethane solution the usual way gave the desired intermediate,N-(2-chloro-5-pyridylmethyl)-N′-(1-methyl-4-pyrazolylmethyl)ethylenediamineas a viscous oil. The yield was 23.5 g.

n_(D) ²⁰1.5655

In the same way as in Example 47, the following compounds, for example,were produced.

N-(3-pyridylmethyl)-N′-(2chloro-5-pyridylmethyl)ethylenediamine

n_(D) ²⁰1.5846

N-(3-methyl-5-isoxazolylmethyl)-N′-(1-methyl-4-pyrazolylmethyl)trimethylenediamine

n_(D) ²⁰1.5224

EXAMPLE 48

A solution of 7 g of 5-bromomethyl-3-methylisoxazole in 20 ml ofacetonitrile was added dropwise to a solution of 12.2 g of2-aminoethanol in 100 ml of acetonitrile below 10° C. After stirring fora while at room temperature, the acetonitrile and excess-2-aminoethanolwere removed under reduced pressure. Chloroform was added to theresidue, and it was washed with a small quantity of water. The treatmentof the chloroform solution the usual way gave the desired2-(2-methyl-5-isoxazolylmethylamino)ethanol. The yield was 4.4 g.

n_(D) ²⁰1.5130

In the same way as in Example 48, the following compounds, for example,were produced.

3-(2-chloro-5-pyridylmethylamino)propanol

n_(D) ²⁷1.5391

N-(4-pyridylmethyl)ethanolamine

bp. 148-150° C./3 mmHg

EXAMPLE 49

To a solution of 15.6 g of 2-(3-methyl-5-isoxazolylmethylamino)ethanolin 100 ml of chloroform was added catalytic pyridine and then 15 g ofthionylchloride at room temperature. After the addition, the mixture wasrefluxed for 30 minutes, and the evaporation of volatile material invaccum yielded crude chlorinated compound as its hydrochloride.

mp. 136-139° C.

An ethanolic potassium hydrosulfide solution was prepared by saturatinghydrogen sulfide gas in a solution of 13.4 g of potassum hydroxide in120 ml of ethanol. To the resulting solution was added portionwise theabove chloride hydrochloride at 25-30° C. With stirring. The reactionmixture was warmed up slowly, then was stirred for 2 hours at 60° C.After cooling to room temperature, inorganic salt was quickly filteredoff with suction. The solvent was removed from the filtrate underreduced pressure to give 2-(3-methyl-5-isoxazolylmethylamino)ethanethiol(12.9 g) as an oil.

n_(D) ²⁵1.5490

In the same way as in Example 49, the following compound, for example,was produced.

2-(2-methyl-5-pyrazinylamino)ethylmercaptan

n_(D) ²⁸1.5581

EXAMPLE 50

2.72 g of ethylenetrithiocarbonate and 2.52 g of dimethylsulfate weremixed and heated to 100° C. for 1 hour. 10 ml of acetic acid and 2.02 gof triethylamine were added to the resulting2-methylmercapto-1,3-dithiolaniummethylsulfate. 2.6 g of2,2,2-trifluoronitroethane was then added dropwise to the mixture withcooling in an ice bath. The whole mixture was heated slowly to 100° C.and maintained at this temperature for 4 hours. After standing overnightat room temperature, 100 ml of water was added to the reaction mixture.The precipitated crystal was filtered and recrystallized from ethanol togive 1-nitro-2,2-ethylenedimercapto-1-trifluoromethylethylene. The yieldwas 4.35 g.

mp. 130-133° C.

EXAMPLE 51

To a solution of 13.1 g of 1-nitro-2-pentanone in 200 ml ofdimethylsulfoxide was added dropwise 44 g of 20% sodium hydroxidesolution at 10-20° C. 12 g of carbon disulfide was then added dropwiseto the solution at 10° C. and the mixture was stirred for 2 hours at0-10° C. 57 g of methyliodide was dropped into the mixture with icecooling and the reaction mixture was allowed to stand overnight at roomtemperature. This was then poured into ice water and the organic layerwas extracted with dichloromethane. The extract was washed with water afew times, and after removing the solvent the residue was purified bychromatography on a silicagel column to give desired1-butyroyl-1-nitro-2,2-bis(methylthio)ethylene. The yield is 3.0 g.

n_(D) ²²1.5880

In the same way as in Example 51, the following compound, for example,was produced.

1-benzenesulfonyl-1-nitro-2,2-bis(methylthio)ethylene

n_(D) ²⁰1.5868

EXAMPLE 52

2.5 g of sodium hydride 60% in oil was added in small portions to asolution of 3.9 g of 2-nitroiminoimidazolidine in dry dimethylformamide.After the addition, the mixture was stirred until the generation ofhydrogen gas ceased. The mixture was cooled at −5° C. and 4.7 g ofphenyl chloroformate was added dropwise below 0° C. After stirring for 1hour at room temperature, the reaction mixture was poured into icewater, adjusted to pH 7, and extracted with dichloromethane. The whitecrystals which remained after removing the dichloromethane, and washingwith ether were 1-(phenoxycarbonyl)-2-nitroiminoimidazolidine andweighed 5.1 g.

mp. 171-175° C.

In the same way as in Example 52, the following compounds, for example,were produced.

1-(2-methyl-5-nitrobenzenesulfonyl)-2-(nitroimino)imidazolidine

mp. 193-197° C.

1-(2,4-dichlorobenzoyl)-2-(nitroimino)imidazolidine

mp. 184-186° C.

EXAMPLE 53

A solution of 3.9 g of 2-nitroiminoimidazolidine and 4.6 g of3-chlorophenylisocyanate in 80 ml of dry acetonitrile was refluxed for 3hours. After cooling to room temperature, the precipitated crystals werefiltered, and washed with ether to give desired1-(3-chlorophenylcarbamoyl)-2-nitroiminoimidazolidine. The yield was 4.7g.

mp. 214-216° C.

Use Example

Comparative compound A-1:

(Compound described in West German OLS No. 2,514,402)

Comparative compound A-2:

(described in Japanese Laid-Open Patent Publication No. 196877/1984))

Comparative compound A-3:

(described in the same patent document as above)

Comparative Compound A-4:

(Compound described in Can. J. Chem., vol. 38, pages 1787-1796)

EXAMPLE 54

Test on Nephotettix cincticeps having resistance to organophosphorusagents:

Preparation of a test chemical

Solvent: 3 parts by weight of xylene

Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether

To form a suitable preparation, 1 part by weight of the active compoundwas mixed with the aforesaid amount of the solvent containing theaforesaid amount of the emulsifier. The mixture was diluted with waterto a predetermined concentration.

Testing method

Onto rice plants, about 10 cm tall, planted in pots each having adiameter of 12 cm was sprayed 10 ml per pot of the water-dilution ofeach active compound in a predetermined concentration prepared as above.The sprayed chemical was dried, and a wire net having a diameter of 7 cmand a height of 14 cm was put over each pot, and 30 female imagoes ofNephotettix cincticeps showing resistance to organophosphorus agentswere released into the net. The pots were each placed in a constanttemperature chamber and the number of dead insects was examined 2 dayslater, and the kill ratio was calculated.

As the result, for instance, Compound Nos.1, 2, 3, 4, 5, 6, 8, 9, 10,11, 13, 14, 15, 16, 17, 19, 20, 22, 26, 27, 31, 32, 33, 34, 35, 36, 39,65, 66, 75, 76, 105, 164, 290, 304, 323, 336, 340, 396, 409, 431, 444,453, 518, 556, 612, 623, 624, 705, 706, 755, 762, 813, 827, 831, 884showed 100% kill at 8 ppm A.I.

On the other hand, as comparison,

A-1 showed 65% kill at 40 ppm A.I.,

A-2 40% kill at 200 ppm A.I. and 0% kill at 40 ppm A.I.,

A-3 0% kill at 200 ppm A.I., and

A-4 30% kill at 200 ppm A.I.

EXAMPLE 55

Test on planthoppers:

Testing method

A water dilution in a predetermined concentration of the active compoundprepared as in Example 54 was sprayed onto rice plants, about 10 cmtall, grown in pots with a diameter of 12 cm in an amount of 10 ml perpot. The sprayed chemical was dried, and a wire net, 7 cm in diameterand 14 cm tall, was put over each of the pots. Thirty female imagoes ofNilaparvata lugens Stal of a strain which showed resistance toorganophosphorus chemicals were released into the net. The pots wereleft to stand in a constant temperature chamber and the number of deadinsects was examined two days later. The kill ratio was then calculated.

In the same way as above, the kill ratio was calculated on Sogatellaflurcifera Horvuth and organophosphorus-resistant Laodelphax striatellusFallen.

As the result, for instance, Compound Nos. 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 29, 35, 37, 39, 43, 65,70, 75, 79, 146, 164, 230, 303, 308, 324, 331, 350, 396, 409, 424, 453,518, 529, 550, 556, 579, 612, 623, 624, 649, 701, 705, 706, 755, 756,758, 848 showed 100% kill at 40 ppm A.I. against each planthopper.

On the other hand, as comparison, A-1 showed, at 40 ppm A.I., 50% killagainst N. lugens, 40% kill against S. furcifera and L. striatellus, A-2at 200 ppm A.I. 30% kill against N. lugens, 20% kill against L.striatellus and 50% kill against S. furcifera, and at 40 ppm A.I. 0%kill against each planthopper, A-3 at 200 ppm A.I. 0% kill against eachplanthopper, and A-4 at 200 ppm A.I. 100% kill ratio against N. lugens,0% kill against L. striatellus and S. furcifera.

EXAMPLE 56

Test on Myzus persicas (green peach aphids) having resistance toorganophosphorus chemicals and carbamate chemicals:

Testing method

Green peach aphids which had been bred and had resistance toorganophosphorus chemicals and carbamate chemicals were inoculated oneggplant seedlings (black elongate eggplants), about 20 cm tall, grownin unglazed pots having a diameter of 15 cm (about 200 aphids perseedling). One day after the inoculation, a water dilution of eachactive compound at a predetermined concentration prepared as in Example54 as sprayed in a sufficient amount onto the plants using a spray gun.After the spraying, the pots were left to stand in a greenhouse at 28°C. Twenty-four hours after the spraying, the kill ratio was calculated.For each compound, the test was carried out through two replicates.

As the results, for instance, compound Nos. 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 24, 25, 26, 27, 28,29, 30, 31, 32, 33, 35, 71, 74, 75, 98, 105, 164, 230, 231, 373, 396,409, 518, 529, 550, 556, 579, 612, 623, 624, 649, 705, 706, 755 756,758, 763, 831 showed 100% kill at 200 ppm A.I.

On the other hand, A-1 showed 80% kill at 1000 ppm A.I. and 30% kill at200 ppm A.I.,

A-3 60% kill at 1000 ppm A.I. and 0% kill at 200 ppm A.I., and

A-4 60% kill at 1000 ppm A.I., 0% kill at 200 ppm A.I.

Examples 54, 55 and 56 are typical examples of insecticidal uses, andthe compounds of this invention exemplified herein are also typicalexamples. It should be understood that the present invention is not tobe limited to them alone.

What is claimed is:
 1. A compound of the formula

in which n represents 0 or 1, R¹, R², R⁵ and R⁶ independently representa hydrogen atom or an alkyl group, R³ and R⁴ independently represent ahydrogen atom, a hydroxy group or an alkyl group, where n represents 1,then R² may form a single bond, together with R⁵, X represents a sulfuratom, an oxygen atom,

or

R⁷ represents a hydrogen atom, a halogen atom, a hydroxy group, analkoxy group, a benzyloxy group, an alkyl group which may be substitutedby at least one member selected from the class consisting of alkoxygroups, alkylthio groups, a cyano group, halogen atoms, dialkylaminogroups and trialkylsilyl, an alkenyl group which may be substituted by ahalogen atom, an alkynyl group which may be substituted by a halogenatom, a phenyl group which may be substituted by an alkyl group and/or ahalogen atom, a benzyl group which may be substituted by at least onemember selected from the class consisting of a methyl group, a methoxygroup, halogen atoms, halomethyl groups, halomethoxy groups and a nitrogroup, a formyl group, an alkenylcarbonyl group, an alkylcarbonyl groupwhich may be substituted by at least one member selected from the classconsisting of alkoxy groups, a phenoxy group, alkylthio groups, andhalogen atoms, a benzoyl group which may be substituted by at least onemember selected from the class consisting of halogen atoms, alkylgroups, halomethyl groups, alkoxy groups, haloalkoxy groups and a nitrogroup, a benzylcarbonyl group which may be substituted by an alkyl groupand/or a halogen atom, an alkoxycarbonyl group which may be substitutedby a halogen atom, an alkylthiocarbonyl group, a phenoxycarbonyl groupwhich may be substituted by at least one member selected from the classconsisting of methyl group, a methoxy group, halomethyl group,halomethoxy groups, halogen atoms and a nitro group, aphenylthiocarbonyl group which may be substituted by a halogen atomand/or an alkyl group, a benzyloxycarbonyl group, a monoalkyl- ordialkyl-aminocarbonyl group, a phenylaminocarbonyl group which may besubstituted by at least one member selected from the class consisting ofalkyl groups, haloalkyl groups and halogen atoms, a benzoylaminocarbonylgroup which may be substituted by an alkyl group and/or a halogen atom,a phenylsulfonylaminocarbonyl group which may be substituted by an alkylgroup and/or a halogen atom, a phenylthio group which may be substitutedby an alkyl group and/or a halogen atom, an alkylsulfonyl group whichmay be substituted by a halogen atom, a phenylsulfonyl group which maybe substituted by at least one member selected from the class consistingof alkyl groups, halogen atoms and a nitro group, an alkylcarbonylmethylgroup, a phenacyl group which may be substituted by a halogen atomand/or an alkyl groups, an organophosphono group, anorganothionophosphono group, —CH₂W or —CO—W, W represents a 5 to 6membered heterocyclic group, containing at least one hetero atomselected from the class consisting of an oxygen atom, a sulfur atom anda nitrogen atom, which may be substituted by at least one memberselected from the class consisting of halogen atoms, alkyl groups andhaloalkyl groups, R⁸ represents a hydrogen atom, an alkyl group, an arylgroup or a benzyl group, Y represents a nitrogen atom or

R⁹ represents a hydrogen atom, a halogen atom, a hydroxy group, analkoxy group, a benzyloxy group, an alkyl group which may be substitutedby at least one member selected from the class consisting of halogenatoms, a hydroxy group, alkoxy groups, alkylthio groups, a cyano group,mono- or di-alkylamino groups, alkylcarbonyl groups, alkoxycarbonylgroups and phenoxycarbonyl groups, an alkenyl group which may besubstituted by a halogen atom, an alkynyl group, a phenyl group whichmay be substituted by an alkyl group and/or a halogen atom, analkylcarbonyl group which may be substituted by a halogen atom, analkenylcarbonyl group, a benzoyl group which may be substituted by atleast one member selected from the class consisting of halogen atoms,alkyl groups and alkoxy groups, an alkoxycarbonyl group which may besubstituted by a halogen atom, an alkkylthiocarbonyl group, aphenoxycarbonyl group which may be substituted by at least one memberselected from the class consisting of halogen atoms, alkyl groups,alkoxy groups and a nitro group, a phenylthiocarbonyl group which may besubstituted by an alkyl group and/or a halogen atom, aphenylthiocarbonyl group which may be substituted by an alkyl groupand/or a halogen atom, a benzyloxycarbonyl group, a benzoylaminocarbonylgroup which may be substituted by an alkyl group and/or a halogen atom,a phenylsulfonylaminocarbonyl group which may be substituted by an alkylgroup and/or a halogen atom, an alkylsulfonylaminocarbonyl group, analkylthio group, an alkylsulfonyl group which may be substituted by ahalogen atom, a phenylthio group which may be substituted by an alkylgroup and/or a halogen atom, a phenylsulfonyl group which may besubstituted by an alkyl group and/or a halogen atom, in addition, R⁹ mayform a bis-form of the formula (I), via a methylene group, R representsa hydrogen atom or an alkyl group, and z represents a 5 to 6 memberedheterocyclic group containing at least one hetero atom selected from theclass consisting of an oxygen atom, a sulfur atom and a nitrogen atom,which may be subsituted by at least one member selected from the classconsisting of halogen atoms, alkyl groups, haloalkyl groups, a nitrogroup, a cyano group, alkoxy groups, alkylthio groups, alkylsulfinylgroups, alkylsulfonyl groups, alkenyl groups, haloalkoxy group,haloalkylthio groups, haloalkenyl groups, acylamino groups,haloacylamino groups, alkoxycarbonyl groups, a thiocyanato group,alkynyl groups, an amino group, alkylamino groups, dialkylamino groups,a carboxy group, a hydroxy group, a mercapto group, cycloalkyl groups,an oxo group, a thioxo group, haloalkenylthio groups, alkoxyalkylgroups, alkoxycarbonylamino groups, a carbamoyl group, acyl groups,alkylaminocarbonyl groups, dialklaminocarbonyl groups, a formyl group,aryl groups optionally substituted by a substituent selected from theclass consisting of halogen atoms, alkyl groups, halogenoalkyl groups,alkoxy groups, a nitro group and a cyano group, aryloxy groupsoptionally substituted by a substituent as shown for the above arylgroups, and aralkyl groups optionally substituted by the samesubstituent as that shown for the aryl groups, provided that where R¹,R², R³, R⁴, R⁵ and R⁶ represent hydrogen atoms simultaneouly, Xrepresents

and Y represents

then Z does not stand for a pyridyl group.
 2. A compound according toclaim 1, in which R¹, R², R⁵ and R⁶ independently represent a hydrogenatom or an alkyl group having 1 to 4 carbon atoms, R³ and R⁴independently represent a hydrogen atom, a hydroxy group or an alkylgroup having 1 to 4 carbon atoms, X represents a sulfur atom, an oxygenatom,

or

R⁷ represents a hydrogen atom, a fluorine atom, a chlorine atom, abromine atom, a hydroxy group, an alkoxy group having 1 to 4 carbonatoms, a benzyloxy group, an alkyl group having 1 to 4 carbon atomswhich may be substituted by at least one member selected from the classconsisting of alkoxy groups having 1 to 4 carbon atoms, alkylthio groupshaving 1 to 4 carbon atoms, a cyano group, a fluorine atom, a chlorineatom, a bromine atom, a dimethylamino group and trimethylsilyl, analkenyl group having 2 to 3 carbon atoms which may be substituted by achlorine atom, an alkynyl group having 2 to 3 carbon atoms, a benzylgroup which may be substituted by at least one member selected from theclass consisting of a methyl group, a methoxy group, a fluorine atom, achlorine atom, a bromine atom and a nitro group, a formyl group, analkenylcarbonyl group having an alkenyl with 2 to 3 carbon atoms, analkyl group having 1 to 5 carbon atoms which may be substituted by atleast one member selected from the class consisting of a methoxy group,a phenoxy group, a fluorine, chlorine and bromine atom, a benzoyl groupwhich may be substituted by at least one member selected from the classconsisting of a fluorine atom, a chlorine atom, a bromine atom, a methylgroup, a trifluoromethyl group, a methoxy group, a difluoromethoxygroup, a trifluoromethoxy group and a nitro group, a benzylcarbonylgroup which may be substituted by at least one member selected from theclass consisting of a fluorine atom, a chlorine atom and a bromine atom,an alkoxycarbonyl group having an alkyl with 1 to 4 carbon atoms whichmay be substituted by a fluorine atom and/or a chlorine atom, analkylthiocarbonyl group having an alkyl with 1 to 4 carbon atoms, aphenoxycarbonyl group which may be substituted by at least one memberselected from the class consisting of a methyl group, a fluorine atom, achlorine atom and a bromine atom, a phenylthiocarbonyl group which maybe substituted by at least one member selected from the class consistingof a methyl group, a fluorine atom, a chlorine atom and a bromine atom,a benzyloxycarbonyl group, a dimethylaminocarbonyl group, aphenylaminocarbonyl group which may be substituted by at least onemember selected from the class consisting of a methyl group, a fluorineatom, a chlorine atom, and a bromine atom, a benzoylaminocarbonyl groupwhich may be substituted by at least one member selected from the classconsisting of a methyl group, a fluorine atom, a chlorine atom and abromine atom, a phenylsulfonylaminocarbonyl group which may besubstituted by at least one member selected from the class consisting ofa fluorine atom, a chlorine atom and a bromine atom a phenylthio group,an alkylsulfonyl group which may be substituted by a fluorine atomand/or a chlorine atom, a phenylsulfonyl group which may be substitutedby at least one member selected from the class consisting of a methylgroup, a fluorine atom, a chlorine atom, a bromine atom and a nitrogroup, a methylcarbonylmethyl group, a phenacyl group which may besubstituted by a fluorine atom and/or a chlorine atom, anorganophosphono group, an organothionophosphono group, —CH₂—W or —CO—W,W represents a 5 to 6 membered hetercyclic group, containing one or twohetero atoms selected from the class consisting of an oxygen atom, asulfur atom and a nitrogen atom, which may be substituted by at leastone member selected from the class consisting of a fluorine atom, achlorine atom, a bromine atom and alkyl groups having 1 to 4 carbonatoms, R⁸ represents a hydrogen atom, an alkyl group having 1 to 4carbon atoms, a phenyl group or a benzyl group, Y represents a nitrogenatom or the following

R⁹ represents a hydrogen atom, a fluorine atom, a chlorine atom, abromine atom, a hydroxy group, an alkoxy group having 1 to 4 carbonatoms, a benzyloxy group, an alkyl group having 1 to 4 carbon atomswhich may be substituted by at least one member selected from the classconsisting of a fluorine atom, a chlorine atom, a hydroxy group, analkoxy group having 1 to 2 carbon atoms, alkylthio groups having 1 to 2carbon atoms, a cyano group, a dimethylamino group, alkylcarbonyl groupshaving an alkyl with 1 to 2 carbon atoms and alkoxycarbonyl groupshaving an alkyl with 1 to 2 carbon atoms, an alkenyl group having 2 to 3carbon atoms, a phenyl group, an alkylcarbonyl group having an alkylwith 1 to 4 carbon atoms which may be substituted by at least one memberselected from the class consisting of a methoxy group, a chlorine atomand a fluorine atom, an alkenylcarbonyl group having an alkenyl with 2to 3 carbon atoms, a benzoyl group which may be substituted by at leastone member selected from the class consisting of a fluorine atom, achlorine atom, a bromine atom, a methoxy group and a methyl group, analkoxycarbonyl group which may be substituted by a fluorine atom and/ora chlorine atom, an alkylthiocarbonyl group having an alkyl with 1 to 4carbon atoms, a phenoxycarbonyl group which may be substituted by atleast one member selected from the class consisting of a fluorine atom,a chlorine atom, a bromine atom, a methyl group, a methoxy group and anitro group, a phenylthiocarbonyl group, a benzyloxycarbonyl group, abenzoylaminocarbonyl group which may be substituted by at least onemember selected from the class consisting of a methyl group, a fluorineatom, a chlorine atom and a bromine atom, a phenylsulfonylaminocarbonylgroup which may be substituted by at least one member selected from theclass consisting of a methyl group, a fluorine atom, a chlorine atom anda bromine atom, an alkylsulfonylaminocarbonyl group having an alkyl with1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, analkylsulfonyl group which may be substituted by a fluorine atom and/or achlorine atom, a phenylthio group which may be substituted by at leastone selected from the class consisting of a methyl group, a fluorineatom, a chlorine atom and a bromine atom, or a phenylsulfonyl groupwhich may be substituted by at least one member selected from the classconsisting of a methyl group, a fluorine atom, a chlorine atom and abromine atom, in addition, R⁹ may form a bis-form of the formula (I),via a methylene group, R represents a hydrogen atom or a methyl group,and Z represents a 5 to 6 membered heterocyclic group, containing one tothree hetero atoms selected from the class consisting of an oxygen atom,a sulfur atom and a nitrogen atom, at least one of which is a nitrogenatom, which may be substituted by at least one member selected from theclass consisting of a fluorine atom, a chlorine atom, a bromine atom,alkyl groups having 1 to 4 carbon atoms which may be substituted by afluorine atom and/or a chlorine atom, a nitro group, a cyano group,alkylsulfinyl groups having 1 to 4 carbon atoms, alkylsulfonyl groupshaving 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atomswhich may be substituted by a fluorine atom and/or a chlorine atom,alkylthio groups having 1 to 4 carbon atoms which may be substituted bya fluorine atom and/or a chlorine atom, alkenyl groups having 2 to 3carbon atoms which may be substituted by a chlorine atom, an acetamidegroup which may be substituted by a fluorine atom and/or a chlorineatom, alkoxycarbonyl groups having an alkyl with 1 to 4 carbon atoms, athiocyanato group, alkynyl groups having 2 to 4 carbon atoms, an aminogroup, a methylamino group, a dimethylamino group, an acetyl group, aformyl group, a carboxy group, a hydroxy group, a mercapto group,cycloalkyl groups having 3 to 7 carbon atoms, an oxo group, a thioxogroup, alkenylthio groups substituted by a fluorine atom, a chlorineatom and/or a bromine atom, alkoxyalkyl groups having 2 to 4 carbonatoms in total, alkylaminocarbonyl groups having an alkyl with 1 to 2carbon atoms, dialkylaminocarbonyl groups having an alkyl with 1 to 2carbon atoms, a phenyl group, a phenoxy group and a benzyl group,provided that where R¹, R², R³, R⁴, R⁵ and R⁶ represent hydrogen atomssimultaneously, X represents

and Y represents

then Z does not stand for a pyridyl group.
 3. A compound according toclaim 1, in which R¹, R², R⁵ and R⁶ independently represent a hydrogenatom or a methyl group, R³ and R⁴ independently represents hydrogen atomor a methyl group, X represents a sulfur atom, an oxygen atom,

or

R⁷ represents a hydrogen atom, an alkyl group which may be substitutedby at least one member selected from the class consisting of a methoxygroup, an ethoxy group, a methylthio group, an ethylthio group, a cyanogroup, a fluorine atom, a chlorine atom and a trimethylsilyl group, anallyl group which may be substituted by a chlorine atom, a propargylgroup, a benzyl group which may be substituted by a methyl group and/ora chlorine atom, a formyl group, a vinylcarbonyl group, an alkylcarbonylgroup having an alkyl with 1 to 3 carbon atoms which may be substitutedby at least one member selected from the class consisting of a methoxygroup, a phenoxy group and a chlorine atom, a benzoyl group which may besubstituted by at least one member selected from the class consisting ofa chorine atom, a bromine atom, a methyl group, a trifluoromethyl group,a methoxy group and a nitro group, a benzylcarbonyl group which may besubstituted by a chlorine atom, an alkoxycarbonyl group having an alkylwith 1 to 2 carbon atoms which may be substituted by a fluorine atomand/or a chlorine atom, an alkylthiocarbonyl group having an alkyl with1 to 2 carbon atoms, a phenoxycarbonyl group which may be substituted bya methyl group and/or a chlorine atom, a phenylthiocarbonyl group whichmay be substituted by a chlorine atom, a benzyloxycarbonyl group, adimethylaminocarbonyl group, a phenylaminocarbonyl group, abenzoylaminocarbonyl group, a phenylsulfonylaminocarbonyl group whichmay be substituted by a methyl group and/or a chlorine atom, aphenylthio group, a methylsulfonyl which may be substituted by achlorine atom, a phenylsulfonyl group which may be substituted by amethyl group, a methylcarbonylmethyl group, a phenacyl group which maybe substituted by a chlorine atom, O,O-diethylthionophosphone group,O-ethyl-S-n-propylthiolophosphono group, —CH₂—W or —CO—W, W represents a5 to 6 membered heterocyclic group, containing one or two hetero atomsselected from the class consisting of an oxygen atom, a sulfur atom anda nitrogen atom, which may be substituted by a fluorine atom, a chlorineatom, a bromine atom and a methyl group, R⁸ represents a hydrogen atom,a methyl group, a phenyl group or a benzyl group, Y represents anitrogen atom or

R⁹ represents a hydrogen atom, a chlorine atom, a bromine atom, ahydroxy group, a methoxy group, a benzyloxy group, an alkyl group whichmay be substituted by at least one member selected from the classconsisting of a fluorine atom, a chlorine atom, a hydroxy group, amethoxy group, a cyano group, a dimethylamino group, an acetyl group anda methoxycarbonyl group, an allyl group, a phenyl group, an acetyl groupwhich may be substituted by a chlorine atom, a vinylcarbonyl group, anallylcarbonyl group, a benzoyl group, an alkoxycarbonyl group having analkyl with 1 to 2 carbon atoms which may be substituted by a fluorineatom, n-butylthiocarbonyl group, a phenoxycarbonyl group which may besubstituted by a chlorine atom and/or a methyl group, aphenylthiocarbonyl group, a benzyloxycarbonyl group, abenzoylaminocarbonyl group which may be substituted by a chlorine atom,a phenylsulfonylaminocarbonyl group which may be substituted by a methylgroup, a methylsulfonylaminocarbonyl group, a propylthio group, amethylsulfonyl group which may be substituted by a fluorine atom and/ora chlorine atom, a phenylthio group which may be substituted by achlorine atom, or a penylsulfonyl group, in addition, R⁹ may form abis-form of the formula (I), via a methylene group, R represents ahydrogen or a methyl group, and Z represents a 5 to 6 memberedheterocyclic group, containing one to three hetero atoms selected fromthe class consisting of an oxygen atom, a sulfur atom and a nitrogenatom, at least one of which is a nitrogen atom, which may be substitutedby at least one member selected from the class consisting of a fluorineatom, a chlorine atom, a bromine atom, a methyl group, fluoroalkylgroups having 1 to 2 carbon atoms, a methoxy group, a methylthio group,a methylsulfinyl group, a methylsulfonyl group, a nitro group, a cyanogroup, a trifluoromethoxy group, a trifluoromethylthio group, an allylgroup, an acetamide group, a methoxycarbonyl group, an acetyl group, aformyl group and a carboxyl group, provided that where R¹, R², R³, R⁴,R⁵ and R⁶ represent hydrogen atoms simultaneously, X represents

and Y represents

then Z does not stand for a pyridyl group.
 4. An insecticidalcomposition comprising an insecticidally effective amount of a compoundaccording to claim 1 in admixture with a diluent.
 5. A method ofcombating insects which comprises applying to said insects or to aninsect habitat an insecticidally effective amount of a compoundaccording to claim 1.